ELECTRON-DEFICIENT PORPHYRINS

by

YUICHI TERAZONO

B . E n g . , K u m a m o t o University, Japan, 1987

M . E n g . , K u m a m o t o University, Japan, 1989

A THESIS SUBMITTED I N PARTIAL F U L F I L L M E N T O F

THE REQUIREMENTS F O RT H E D E G R E E O F

DOCTOR OF PHILOSOPHY

in

T H E F A C U L T Y O F G R A D U A T E STUDIES

Department o f Chemistry

W e accept this thesis as c o n f o r m i n g

to the requited standard

T H E UNIVERSITY O F BRITISH C O L U M B I A

July 2001

(C) Y u i c h i T e r a z o n o , 2001
 In presenting this thesis in partial fulfilment of the requirements for an advanced
degree at the University of British Columbia, I agree that the Library shall make it
freely available for reference and study. I further agree that permission for extensive
copying of this thesis for scholarly purposes may be granted by the head of my
department or by his or her representatives. It is understood that copying or
publication of this thesis for financial gain shall not be allowed without my written
permission.

Department

The University of British Columbia

Vancouver, Canada

DE-6 (2/88)
 11

ABSTRACT

T h e search for effective porphyrin catalysts for oxygenations that m i m i c the functions o f

cytochrome P-450 has led to the synthesis of electron-deficient porphyrins. Novel

P-ttifluoromerhyl-OT^-tetJ:aphenylporphyrins were prepared by the copper assisted

trifluoromethylation using P-bromo-w^o-tetraphenylporphyrins and in-situ generated C F C u via 3

the pyrolysis o f C F C 0 N a / C u I or the metathesis o f trifluoromethylcadmium ( ( C F ) C d

3 2 3 2 +

C F j C d B r / C u B r ) . A l t h o u g h multiple trifluoromethylation was difficult due to the steric bulk o f

the — C F group, the existence o f various ^wo-tetraphenylporphyrins w i t h perfluoroalkyl moieties

3

was affirmed. Partially trifluoromethylated porphyrins H T P P ( C F ) 2 3 2 (

4 6a)
, H TPP(CF ) (
4
2 7a)
, 3 3

H TPP(CF )
2 3 4 (
4 8a)
, and H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 were obtained by trifluoromethylation o f

Zn(TPPBr ) 4 (45b) foUowed by demetallation. Zn(TPP(CF ) ) 3 4 (

4 8b)
, C o ( T P P ( C F ) ) (48e)
3 4

Fe(TPP(CF ) )Cl 3 4 (
4 8f
), and F e ( T P P ( C F ) ( C F C F ) ) C l (52c)
3 3 2 3 were also synthesized from the

corresponding free-base porphyrins. These metalloporphyrins, as well as free-base porphyrins,

were used for the analysis o f the electronic and the steric effects o f the — C F groups o n the 3

Ph C F , Ph C F 3

46a

48a : M= 2H +
F C Ph 5 2 a : M = 2 H +

F C
3 Ph 3

48b : M= Zn(II) 52c : M = Fe(III)Cl

48e : M= Co(II)
48f : M= Fe(III)Cl
 Ill

porphyrin macrocycle by UV-visible and H N M R spectroscopy, cyclic voltammetry, and

l

X-ray crystallography. These analyses not only suggested that novel

p-trifluoromethylporphyrins were electron-deficient but also showed that those porphyrins

take bacteriochlorin-like distorted electronic structures; a fixed 187t-electronic pathway. A n

X-ray crystal structure of 48b revealed severe macrocycle distortion into a saddle shape due to

the steric interaction between the —CF and the meso-phenyl groups. Catalytic oxidations of
3

cyclohexane and cyclohexene using 48f and 52c as catalysts, iodosylbenzene (PhIO) as an

oxidant and the above-mentioned substrates showed that they were not superior to one of the

best porphyrin catalysts, Fe(TDCPPCl )Cl (10d) 8 and porphyrin 48f and 52c were not very

stable in the oxidation runs. Although the prepared novel porphyrins were not satisfactory as

P-450 model compounds, interesting electronic and structural properties of the

zwj-0-tettaphenylporphyrins partially trifluoromethylated at the pyrrolic P-positions of antipodal

pyrroles were revealed. The steric and electronic effects of the —CF groups on the pyrrolic 3

P-positions of zmo-teteaphenylporphyrin were also compared to those of P-methyl analogues

(57a, 58a, 59a, and 59b) in order to compare these effects distincdy.

Ph C H ,

Ph
Ph C H 3
58a

/-IN s ,N=/
Ph—(\ M //-Ph

A r = 2,6-dichlorophenyl
HC 3 Ph 59a : M = 2 H +

59b : M = Zn(II)
 IV

TABLE OF CONTENTS

ABSTRACT n
TABLE OF CONTENTS iv
LIST OF TABLES vii
LIST OF FIGURES viii
LIST OF SCHEMES xi
LIST OF ABBREVIA TIONS xii
NOMENCLATURE xvii
ACKNOWLEDGEMENT xix
CHAPTER I 1
A. I
n t
roduct
i
o n 1
B. Met
a l
o por
p hyr
i
n s as c
yt
och
romeP-
450mo
delc
omp
oun
ds 5
1. Cytochromes P-450 5
a. Distribution, nomenclature, and structure 5
b. Function and mode of action 6
c. Mechanisms of hydrocarbon oxidation 8
(1) Mechanism of alkane hydroxylation 8
(2) Mechanism of alkene epoxidation 9
2. Synthetic metalloporphyrins as P-450 rnirnics 11
a. Structures of porphyrins that appear in this section 11
b. Synthetic methods for the major players in the early development of P-450 mimics
12
(1) Condensation of pyrrole with arylaldehydes 12
(2) p-Perchlorinated and perbrominated meso-arylporphyrins 13
c. Early development of P-450 mimics 14
d. Electron-withdrawing effects on catalytic activities 16
e. Newer generation of electron-deficient porphyrins 22
(1) P-Perfluoro-meso-tetraatylporphyrins 22
(2) P-Nitro-meso-tetrakis(2,6-dichlorophenyl)porphyrins 25
(3) meso-Tetrakis(perfluoroalkyl)porphyrins 28
3. Design concept for a new P-450 mimic 30
a. Basic concept 30
b. Potential advantages of trifluoromethyl substituents 31

C. Sy
n t
h e
tc
i s
tr
ate
g y for P-
t
ri
fl
u or
o met
h yl
a t
i
o n of me
so-
t
e t
r
a phe
n y
p
lor
p hy
rn
i 32
1. Brief overview of trifluoromethylation 32
a. Fluorination of an existing aryl substituent (Scheme 1-3) 33
b. Introduction of trifluoromethyl groups 33
(1) Transfer of CF " (Scheme l-4(a))
3 33
 (2) Transfer of C F (Scheme l-4(b))
3
+
, 34
2. C o p p e r assisted trifluoromethylation 35
a. C F C u from pyrolysis o f sodium trifluoromethyl acetate i n the presence o f Cu(I)
3

halide 35
b. C F C u f r o m metathesis o f trifluorometiiylcadmium w i t h Cu(I) halide
3 37
(1) Trifluoromethylation 37
(2) Synthesis of trifluoromethylcadmium 37

D . Analysis of porphyrins 38
1. U V - v i s i b l e absorption spectroscopy 38
a. Characteristics o f U V - v i s i b l e absorption spectra o f porphyrins and
metalloporphyrins 38
b. Electron-withdrawing effects o n U V - v i s i b l e absorption spectra 41
2. R e d o x potentials o f porphyrins 43
a. General redox properties o f porphyrins i n non-aqueous media 43
(1) Technique, solvent, and supporting electrolytes 43
(2) Porphyrin ring redox properties in free-base and metalloporphyrins 44
(3) Iron porphyrins 44
b. Effects o f substituents o n the redox potentials o f derivatives o f T P P 47
(1) Aryl-ring-substituted T P P s 47
(2) fJ-Substituted TPPs 49
(3) Conclusion 54
3. H N M R spectroscopy
l
55
a. P o r p h y r i n ring current effect 55
b. Concentration effect 55
c. N - H tautomerism 57
4. Spectrophotometric titration 59
a. Evaluation o f p K , o f N H 59
b. Determination o f central metal — ligand b i n d i n g constant 61

E . Goals of this thesis 63

CHAPTER II 64
A. Synthesis of P-trifluotomethyl- and P-methyl-weso-tetraphenylporphyrins 64
1. Trifluoromethylation 65
a. Synthesis o f precursors 66
b. Trifluoromethylation by pyrolysis o f C F C 0 N a / C u l
3 2 67
(1) Reaction using Cu(TPPBr ) (7c) 8 67
(2) Reactions using M T P P B r ( M = Zn(II), Cu(II), and Ni(II)) (45b,45c,and 45d)
4 69
c. Trifluoromethylation by C F C u generated by the metathesis o f
3

tiifluorometiiylcadmium and C u B r 72
(1) Preliminary experiments 72
(2) Optimization of the yield for P-tetrakis(trifluoromethyl)-meso-tetraphenylporphyrin....76
2. Methylation 88
3. Metallation 90
a. Synthesis o f Zn(II) and Co(II) complex o f 48 91
b. Synthesis o f Fe(III) complexes o f 48 and 52 92
4. Summary 95

B. Analysis of P-trifluoromethyl-weso-tetraphenylporphyrins..../ 95
 VI

1. UV-visible spectra of synthesized novel porphyrins 97

a. Free-base porphyrins 98
(1) UV-visible spectra in C H C 1
2 2 98
(2) Absorbance vs. concentration of 48a • 109
b. UV-visible spectra of metalloporphyrins 110
2. N M R spectroscopy 116
a. Determination of electronic pathway of P-tdfluoromethylporphyrins 117
b. Unusual ' H N M R chemical shift for pyrrolic p-protons of H T P P ( C F ) (48a)
2 3 4 126
3. Redox potentials 134
a. Free-base P-trifluoromethyl-^m-tetraphenylporphyrins 136
b. Zn(II) porphyrins 144
c. Fe(III) porphyrins 151
4. Crystal structures 153
a. Preparation of the crystals and crystallographic data 153
b. Structure details 155
(1) Core size, Z n displacement, and axial coordination 155
(2) Effects o f antipodal P-substitation 161
(3) Macrocycle distortion 164
(4) Orientation of the axial ligand 169
5. Specttophotometric titration 172
a. Titration of 48a with strong organic bases in CH Ci2
2 173
(1) Titration with D B U 173
(2) Titration with E t N
3 176
b. Titration of Co(rPP(CF ) ) (48e) with pyridine and imidazole
3 4 176
6. Summary 182

C. Catalytic oxidation of cyclohexane and cyclohexene 184

CHAPTER III 188

A. Conclusions 188

B. Future work 189

CHAPTER IV 195

A. Chemicals 195

B. Instrumentation 195

C. Procedures 197

D . Preparation of materials 202

REFERENCES 220

APPENDICES 233

A. UV-visible spectra of diacids of 48a and 59a 233

B. Crystallographic Data 234

 vii

LIST O F T A B L E S

Table 1-1. Yields o f typical (3-perhalogenation reactions p.14

Table 1-2. Relationship between catalyst i r o n redox potentials a n d activities 19
Table 1-3. O" values for different substituents 31
Table 1-4. T h e first reduction and oxidation potentials for 36 - 39 54
Table 1-5. F o r m a t i o n constants for pyridine b i n d i n g i n C H C 1 at 25 ° C 2 2 62

Table 2-1. Results o f trifluoromethylation by the pyrolysis m e t h o d 71

Table 2-2. Trifluoromethylation by metathesis using M T P P B r (45) 4 75
Table 2-3. Products obtained by the reaction at 70 ° C for 88 h 78
Table 2-4. R values for metal-free perfluoroalkylated porphyrins
f 79
Table 2-5. Isolated P-perfluoroalkyl-^fo-tetraphenylporphyrins 82
Table 2-6. C o m p a r i s o n o f U V - v i s i b l e absorption maxima 99
Table 2-7. U V - v i s i b l e absorption maxima o f metalloporphyrins 114
Table 2-8. C h e m i c a l shift values o f Zn(II) P-tetrasubstituted
wt?.ra-tettaphenylporphyrins 133
Table 2-9. R e d o x potentials o f P-substituted wwo-tetraphenylporphyrins i n C H C 1 . 2 2

140
Table 2-10. R e d o x potentials o f P-substituted ^.r^teteaphenylporphyrin Zn(II)
complexes i n C H C 1 2 2 147
Table 2-11. R e d o x potentials o f Fe(III) porphyrin chloride complexes 152
Table 2-12. Crystallographic data for 45b-(MeOH)-(DMF), 48b-(EtOH) , and 3

59b-(THF) -(CHCl )
16 3 04 154
Table 2-13. Core size, selected b o n d lengths a n d b o n d angles 159
Table 2-14. Cp-Cp b o n d lengths i n antipodally P-tetrasubstituted
^^o-tetraphenylporphyrins 164
Table 2-15. B i n d i n g constants o f Co(II) porphyrins for base b i n d i n g i n i n C H C 1 . . . 182 2 2

Table 2-16. O x i d a t i o n o f cyclohexane and cyclohexene using Fe(III) porphyrins a n d

iodosylbenzene i n C H C 1 2 2 185

Table B-l-a A t o m i c coordinates a n d B for Z n ( T P P ( C F ) ) - ( E t O H )

e q 3 4 234 3

Table B-l-b A n i s o t r o p i c displacement parameters for Z n ( T P P ( C F ) ) - ( E t O H ) 3 236

4 3

Table B-2-a A t o m i c coordinates a n d B for Z n ( T P P B r ) - ( M e O H ) - ( D M F )

c q 4 238
Table B-2-b A n i s o t r o p i c displacement parameters for Z n ( T P P B r ) - ( M e O H ) - ( D M F ) . 2 4 0
4

Table B-3-a A t o m i c coordinates and B for Z n f T T ^ C H ^ - C I H F ) , - ( C H C l )

e q 242 6 3 0 4

Table B-3-b A n i s o t r o p i c displacement parameters for

ZnCrPP(CH ) )-CiHF) -(CHCl ) .
3 4 16 3 0 4 244
 Vlll

LIST O F F I G U R E S

Figure 1-1. P r o t o p o r p h y r i n F X F e complex p.l

Figure 1-2. Examples o f electron-deficient porphyrins 2
Figure 1-3. E x a m p l e o f salen M n ( I H ) complex 3
Figure 1-4. A c t i v e site and hydrophobic pocket o f cytochrome P - 4 5 0 cam 5
Figure 1-5. Catalytic cycle o f cytochrome P-450 7
Figure 1-6. M e c h a n i s m o f alkane hydroxylation by cytochrome P-450 9
Figure 1-7. M e c h a n i s m o f the oxidation o f olefins by cytochrome P-450 10
Figure 1-8. Porphyrins used i n P-450 m o d e l studies 11
Figure 1-9. Reaction o f oxo Fe(FV) porphyrin Tt-cation radical w i t h alkene and
/-BuOOH 18
Figure 1-10. Catalytic cycle for isobutane hydroxylation by 0 2 and 8d proposed by Ellis
and L y o n s 20
Figure 1-11. Synthesis o f p-polynitto-OT^-tefi:alds(2,6-dicUorophenyl)porphyrins 26
Figure 1-12. Synthesis o f wm>-tetJ:aMs(perfluoroalkyi)porphyrins 29
Figure 1-13. R e m o v a l o f water by use o f a toluene-azeotrope i n the
pentafluoroethylation o f a-iodonaphthalene 36
Figure 1-14. U V - v i s i b l e spectra o f « ? ^ - t e t r a p h e n y l p o r p h y r i n s C H C 1 2 2 39
Figure 1-15. Symmetries o f Z n ( T P P ) (2b), H T P P (2a) and [ H T P P ]
2 4
2 +
40
Figure 1-16. E x a m p l e o f the U V - v i s i b l e spectral change by electron-withdrawing
effects 42
Figure 1-17. Cyclic voltammogram o f H T P P (2a) i n C H C 1
2 2 2 45
Figure 1-18. Cyclic voltammogram o f F e ( T P P ) C l (2d) i n C P ^ C h . 46
Figure 1-19. Plot o f E 1 / 2 vs. 4a for the electrode reactions o f H TP(/>-X)P (31a) 2 48
Figure 1-20. First reduction and oxidation potentials vs, # o f C N groups for (a)
H T P P ( C N ) (34a) and (b) C u T P P ( C N ) (34c)
2 S x 51
Figure 1-21. P l o t o f the first oxidation and the first reduction potential for
F e f T P P B r J C l (35a) using P h C N as solvent 52
Figure 1-22. Side view o f the crystal structures o f H T M P (3a), H T M P C 1
2 2 4 (36),
H TMPBr
2 4 (37), and H T M P C 1 (38)
2 8 53
Figure 1-23. 200 M H z H N M R spectrum o f H T P P (2a) i n C D C 1 at 298 K
}
2 3 56
Figure 1-24. P l o t o f ' H chemical shift o f meso-Hvs. porphyrin concentration for 40a. 58
Figure 1-25. Tautomerism i n H T P P (2a) 2 59
Figure 1-26. Relative populations o f 42a and 42b at 200 K i n C D C 1 2 2 60

Figure 2-1. U V - v i s i b l e spectra during trifluoromethylation o f 45b at 70 °C 77

Figure 2-2. U V - v i s i b l e spectra during trifluoromethylation o f 45b at 110 ° C 81
Figure 2-3. 3,4-Dibromopyrrole and 3,4-bis(trifluoromethyl)pyrrole modeled by
HyperChem 84
Figure 2-4. U V - v i s i b l e spectra o f the orange c o m p o u n d and H T P P ( C F ) (48a) 2 3 4 87
Figure 2-5. U V - v i s i b l e spectra o f P-tafluorometiiyl-wwo-tettaphenylporphyrins, (a)46a,
(b)47a, and (c)48a i n C H C 1 2 2 101
Figure 2-6. U V - v i s i b l e spectra o f P-tetrabromo-OTc?j(9-tetraphenylporphyrins (45a) i n
CH C1 2 2 102
 IX

Fi
g ur
e 2-7. a)57a, (b)58a,
UV-visible spectra of P-memyl-w^o-tettaphenylporphyrins, (
and (c)
5 9a in CH C1 2 2 103
Fi
g ur
e 2-8. UV-visible spectra of 52a in C H C 1 106 2 2

Fi
g ur
e 2-9. UV-visible spectra of bacteriochlorin (64) 108
Fi
g ur
e 2-10. UV-visible spectral change of H T P P ( C F ) (48a) Ill 2 3 4

Fi
g ur
e 2-11. UV-visible spectral change of H T P P ( C F , ) ( C F C F ) (52a) 112 2 3 2 3

Fi
g ur
e 2-12. UV-visible spectra of Zn(TPP(CF ) ) (48b) and Co(TPP(CF ) ) (48e) in 3 4 3 4

CH C1 2 2 : 113
Fi
g ur
e 2-13. UV-visible spectra of [Fe(TPP(CF ) )]Cl ( 4 8 f
), [FeTPP(CF ) (CF CF )]Cl 3 4 3 3 2 3

(5 2c )
, and [Fe(TPPBr )]Cl (45e) 4 115
Fi
g ur
e 2-14. 400 M H z *H N M R spectra of H T P P B r (45a) in CDC1 at room 2 4 3

temperature 118
Fi
g ur
e 2-15. 400 M H z ' H N M R spectra of H T P P ( C F ) (47a) in CDC1 at room 2 3 3 3

temperature 120
Fi
g ur
e 2-16. 400 M H z C O S Y spectra of H T P P ( C F ) (47a) 121
2 3 3

Fi
g ur
e 2-17. 18^-electron pathway of H T P P ( C F ) (47a) 2 122 3 3

Fi
g ur
e 2-18. 200 M H z ' H N M R spectra of H T P P ( C F ) (47a) in the presence of and in 2 3 3

the absence of residual water in CDC1 123 3

Fi
g ur
e 2-19. 400 M H z ' H N M R spectra of H T P P ( C H ) (58a) in CDC1 at room 2 3 3 3

temperature 125
Fi
g ur
e 2-20. 200 M H z ' H N M R spectra of (a) H T P P (2a), (b) H T P P B r ( 45a )
, (c) 2 2 4

H T P P ( C F ) (48a) and (d) H T P P ( C H ) (59a) in C D at room

2 3 4 2 3 4 6 6

temperature 127
Fi
g ur
e 2-21. 400 M H z ' H N M R spectra of diacid of (a) H T P P ( C F ) ( 48a)
, (b) 2 3 4

H T P P B r (45a) and (c) H T P P ( C H ) (59a) in T F A - d at room

2 4 2 3 4

temperature 130
Fi
g ur
e 2-22. Structures of (a) [ H T P P ] and (b) [ H T P P ( C H ) ]
4
2+
132 4 3 4
2+

Fi
g ur
e 2-23. Cyclic voltammograms of (a) H T P P ( C F ) (46a) and (b) H T P P ( C F ) 2 3 2 2 3 3

(47a) 137
Fi
g ur
e 2-24. Cyclic voltammograms of H T P P ( C F ) (48a) at different scan rates 2 138 3 4

Fi
g ur
e 2-25. Cyclic voltammograms of (a) H T P P ( C H ) ( 5 7 a), (b) H T P P ( C H ) (58 a2)
, 3 2 2 3 3

and (c) H T P P ( C H ) (59a)

2 3 4 139
Fi
g ur
e 2-26. Redox potentials of (a) H T P P ( C F ) (x = 0 (2a), 2 (
4 6
2 a )
, 3( 4 7 a )
, and 4 3 X

(
4 8a )) and (b) H T P P ( C H ) (x = 0 (2a), 2 (
2 5 7 a), 3(5 8 a
3 )
, and 4 (
X 59 a )
).. 143
Fi
g ur
e 2-27. Energy level diagram for H O M O s and L U M O s of the four generic
metalloporphyrin classes 145
Fi
g ur
e 2-28. (a) Cyclic voltammogram of Zn(TPP(CF ) (
4 8b)
. (b) 4a vs. 1st oxidation 3 4)

and 1st reduction potentials of P-tetrasubstituted meso-

tetraphenylporphyrinato Zn(II) (Zn(TPP) (2b), Zn(TPP(CN) (34b, 4 x=4),
Zn(TPPBr ) ( 45 b), Zn(TPP(CF ) ) (
4 48b )) 3 4 146
Fi
g ur
e 2-29. The H O M O - L U M O gap of P-substituted wao-arylporphyrin Zn(II)
complexes 149
Fi
g ur
e2-
3 0-
4 5b. X-ray crystal structures of 45b-(MeOH)'(DMF) 156
Fi
g ur
e2-
3 0-
4 8b. X-ray crystal structures of 48b- (EtOH) 157 3

Fi
g ur
e2-
3 0-
5 9b. X-ray crystal structures of 59b-(THF) -(CHCl ) 158 16 3 04
 X

Figure 2-31. Schematic illustration of the steric effects of antipodal (3-substituents and
meso-phenyl groups on the macrocycle of (3-tetrasubstituted meso-
tetraphenylporphyrin 163
Figure 2-32. Perpendicular atomic displacements of the Z n porphyrins, relative to the
N mean plane
4 166
Figure 2-33. Orientations of phenyl and C F , groups in 48b 168
Figure 2-34. Orientations of phenyl and C H groups in 59b 3 170
Figure 2-35. UV-visible spectral change in titration of H T P P ( C F ) (48a) with D B U in2 3 4

CH C1 2 2 174
Figure 2-36 Logarithmic analysis of the spectral data for the addition of D B U to
H T P P ( C F ) (48a) in C H C 1
2 3 4 2 2 175
Figure 2-37. UV-visible spectral change in titration of H TPP(CF ) (48a) with E t N in 2 3 4 3

CH C1 2 2 177
Figure 2-38. Titration of Co(TPP(CF ) ) (48e) in C H C 1 with pyridine at 25.0 ° C
3 4 2 178
2

Figure 2-39. Spectral changes in the pyridine addition to Co(TPP(CF ) )-(Py)(48e-(Py)) 3 4

inCH Cl at25.0°C
2 2 179
Figure 2-40. Logarithmic analysis of the spectral data for the addition of pyridine to
Co(TPP(CF ) )(48e) in C H C 1 3 4 2 2 181

Figure 4-1. Electrochemical cell and electrodes 196

Figure 4-2. Possible isomers for (3-tris(tjifluoromemyl)-OTWt9-tetraphenylporphyrin..210

Figure A - l . UV-visible spectra of freebase porphyrins, H T P P ( C F ) (48a) and 2 3 4

H T P P ( C H ) (59a) in C H C 1 and their diacids in C H C 1 containing

2 3 4 2 2 2 2

0.5%(v)TFA 233
 XI

LI
S T OF SCHEMES

S
che
m e 1-1. Synthesis of w^o-tetraarylporphyrins p.12
S
che
m e 1-2. P-Halogenation of /W^ro-tetraarylporphyrin 14
S
che
m e 1-3. Fluorination of an existing aryl substituent 33
S
che
m e 1-4. Introduction of a triiluoromethyl group 34
S
che
m e 1-5. Trifluoromethylation of aromatic halide by pyrolysis of C F C 0 N a 3 2 36

S
che
m e 2-1. Trifluoromethylation strategies 66
S
che
m e 2-2. Trifluoromethylation of P-octabromo-wwo-tetraphenylporphyrinato Cu(II)
(7c) by pyrolysis of C F C 0 N a / C u I
3 2 68
S
che
m e 2-3. Trifluoromethylation of P-tetrabromo-^j'o-porphyrins (45) by pyrolysis of
CF C0 Na/CuI
3 2 70
S
che
m e 2-4. Trifluoromethylation of P-tetrabromo-wi?j"o-porphyrins (45) by metathesis
of C F - C d / C u B r / H M P A
3 74
S
che
m e 2-5. Product distribution in trifluoromethylation of 45b by metathesis at 70, 90,
and 110 °C 85
S
che
m e 2-6. Methylation of 45b 89
S
che
m e 2-7. Insertion of Zn(II) and Co(II) into H T P P ( C F )
2 (48a)
3 4 91
S
che
m e 2-8. Synthesis of Fe(TPP(CF ) )Cl (48f) and Fe(TPPBr )Cl (45e)
3 4 4 93
S
che
m e 2-9. (a)187t-electron pathway of bacteriochlorin (64) and (b) the possible
electronic pathway of p-trifluoromethylporphyrins 108
S
che
m e 2-10. Atom designations used in Table 2-13 155
S
che
m e 2-11. Schematic representation of macrocyclic distortion and axial coordination
in 45b-(MeOH), 59b-(THF), and 48b(EtOH) 171

S
che
m e 3-1. wwo-Tettaltis(2,6-bis(trifluoromethyl)phenyl)porphyrin (66) 192
S
che
m e 3-2. Formation of oxo Fe(rV) porphyrin u-cation radical from Fe(III)
porphyrin and hydrogen peroxide 194
 xii

LIST OF ABBREVIATIONS

Abs. Absorbance
ArCF 3 Trifluoromethyl aryl compound
Arl Iodo aryl compound
B Lewis base
br, bs Broad, broad singlet
BuCN Butyronitrile
t-Bu /-Butyl
Calcd. Calculated
CF -Cd3 C F C d X + (CF ) Cd, X = CI or Br
3 3 2

Cone. Concentrated
5,10,15,20-Tetralds(4-memoxyphenyl)porphyrinatocobalt(Ii)
Co(TP(z>-OCH )P) 3
Co(TPFPPF ) 8 2,3,7,8,12,13,17,18-Octafluoro-5,l 0,15,20-
tetralris(perfluorophenyl)porphyrrnatocobalt(Ii)
Co(TPP(CN) ) 4 2,3,12,13-Tetracyano-5,l 0,15,20-
tetraphenylporphyrinatocobalt(II)
CofTPPFg) 2,3,7,8,12,13,17,18-Octafluoro-5,l 0,15,20-
tettaphenylporphyrmatocobalt(II)
Cu(TPP(CN)0 P-Polycyano-5,10,15,20-tetraphenylporphyrinatocopper(Ii)
Cu(TPP) 5,10,15,20-Tetraphenylporphyrinatocopper(H)
Cu(TPPBr ) 4 2,3,12,13,-Tetrabromo-5,l 0,15,20-
tetraphenylporphyrinatocopper(II)
Cu(TPPBr ) 8 2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-
tetraphenylporphyrinatocopper(II)
Cys Cysteine
d Doublet
DBU l,8-Diazabicyclo[5.4.0]undec-7-ene
DDQ 2,3-Dichloro-5,6-dicyanoquinone
DMF N,N-Dimethylformamide
DMSO Dimethylsulfoxide
E v (1)
2
First half-wave oxidation potential
E £ (1) First half-wave reduction potential
E°; (2) 2 Second half-wave oxidation potential
(2) Second half-wave reduction potential
EI Electron impact
eq. Equimolar
Et£> Diethylether
Et N 3 Trietiiylamine
EtOH Ethanol
F.W. Formula weight
FAB Fast atom bombardment
Fc/Fc +
Ferrocene/ferrocenium
Fe((C F ) P)Cl 3 7 4 Chloro[5,10,15,20-
tetiakis(heptafluoropropyl)porphyrinato]rron(IIi)
Fe(TDCPP)Cl CUoro[5,10,15,20-tetrakis(2,6-
chcHorophenyl)porphyrmato]iron(III)
Fe(TOCPPBrg)Cl CWoro[2,3J3,12,13 17,18-octabromo-5 10,15 20-terj:akis(2,6-
) ) )

cUcMorophenyl)porphyrmato]iron(III)
Fe(TDCPPCl )Cl 8 ChJoro[2,3,7 8,12,13,17,18-octachloro-5,10,15,20-tetrakis(2,6-
)

dicmorophenyl)porphyrinato]iron(III)
Fe(TDCPPF )Cl 8 CMom[2,3JA12,13,17,18-octafluoro-5,10,15,20-tetrakis(2,6-
cUchlorophenyl)porphyrinato]iron(III)
Fe(TMP)Cl C h l o r o ( 5 , l 0,15,20-tetomesitylporphyrinato)iron(III)
Fe(TP(w-X)P)Cl C h l o r o [5,10,15,20-tetrakis (3-substituted
phenyl)porphyrinato]iron(III)
Fe(TP(/)-X)P)Cl Chloro[5,10,15,20-tetrakis(4-substituted
phenyl)porphyrinato]iron(III)
Fe(TPCPP)Cl CUoro[5,10,15,20-tetralds(percUorophenyl)porphyrinato]
Fe(TPCPPCl )Cl 8 Chloro[2,3,7,8,12,13,17,18-octachloro-5,10,15,20-
tettakis(percUorophenyl)porphyrmato]iron(III)
Fe(TPFPP)Cl CUoro[5,10,15,20-teUakis(perfluorophenyl)porphyrinato]iron(
FeCTPFPPBr^Cl C h l o r o [2,3,7,8,12,13,17,18-octachloro-5,l 0,15,20-
tettakis(perfluorophenylphenyl)porphyrinato]iron(III)
FefTPFPPF^Cl Chloro[2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-
tettakis(perfluorophenyl)porphyrinato]iron(IIi)
FeCrPP(CF )3(CF CF ))Cl
3 2 3 C h l o r o [7,8,17 -tris (trifluoromethyl) -18-pentafluoroethyl-
5,10,15,20-tetraphenylporphyrinato]iron(III)
Fe(rPP(CF ) )Cl 3 4 Chloro[7,8,l 7,18-tetxakis(trifluoromethyl)-5,l 0,15,20-
tetraphenylporphyrinato]iron(III)
[FeCrPP(CF ) ] 0 3 4 2 (u-Oxo)bis [2,3,12,13-tetealds(trifluoromemyl)-5,l 0,15,20-
tetraphenylporphyrinatoiron(Iir)]
Fe(TPP(CN) )Cl 4 Chloro(2,3,12,l 3-tetracyano-5,10,l 5,20-
tetraphenylporphyrinato)iron(III)
Fe(TPP)Cl C h l o r o ( 5 , l 0,15,20-tetraphenylporphyrinato)iron(Iir)
Fe(TPPBi )Cl 4 Chloro(7,8,l 7,18-tetrabromo-5,l 0,15,20-
teteaphenylporp>hyrinato)iron(III)
FefTPPBrJCl Chloro(P-polybromo-5,l 0,15,20-tettaphenyporphyrinato)kon(
FetTPPF^Cl Chloro(2,3,7,8,12,l 3,17,18-octafluoro-5,l 0,15,20-
teteaphenylporphyrinato)iron(III)
GC Gas chromatography
h hour(s)
H (CF ) P
2 3 4 5,10,15,20-tettalds(ttifluoromemyl)po]^hyrin
H DPP
2 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin
H TDCPP
2
5,10,15,20-Tetrakis(2,6-dichlorophenyl)porphyrin
H 2 TDCPP(N02) X p-Polynitro-5,10,15,20-tetealds(2,6-dicUorophenyl)porphyrin
H 2 TMP 5,10,15,20-Tetramesitylporphyrin
H 2 TMPBr 4 7,8,17,18-Tetrabromo-5,10,15,20-tetramesitylporphyrin
H 2 TMPBr 8 7,8,17,18-Octabromo-5,l 0,15,20-tetramesitylporphyrin
H TMPC1
2 4 7,8,17,18-Tetrachloro-5,l 0,15,20-tetramesitylporphyrin
H TP(/>-X)P
2 5,10,15,20-Tetrakis(4-substituted phenyl)porphyrin
H TPCPP
2 5,10,15,20-Tettakis(perchlorophenyl)porphyrin
 XIV

H TPFPP
2 5,10,15,20-Tetrakis(perfluorophenyl)porphyrin
H TPP
2 5,10,15,20-Teteaphenylporphyrin
H TPP(CF )
2 3 2 p-Bis(tofluoromethyl)-5,l 0,15,20-teteaphenyporphyrin
H TPP(CF )
2 3 3 7,8,17-Tris(ttifluorornethyl)-5,l 0,15,20-tetraphenyporphyrin
H TPP(CF ) (CF CF )
2 3 3 2 3 7,8,17-Tris(tofluoromethyl)-l 8-pentafluoroethyl-5,l 0,15,20-
teteaphenylporphyrin
H TPP(CF,)
2 4 7,8,17,18-Tettakis(trifluoromethyl)-5,l 0,15,20-
tetraphenyporphyrin
H TPP(CH )
2 3 2 P-Dimethyl-5,10,15,20-tettaphenyporphyrin
H TPP(CH )
2 3 3 7,8,17-Trimethyl-5,l 0,15,20-tetraphenyporphyrin
H TPP(CH )
2 3 4 7,8,17,18-Tetramethyl-5,l 0,15,20-tetraphenyporphyrin
[H TPP(CH ) ]
4 3 4
2+
7,8,17,18-Tetramethyl-5,l 0,15,20-tetraphenyporphyrin
diprotonated dication
H TPP(CN)
2 X P-Polycyano-5,10,15,20-tetraphenylporphyrin
H TPP(X)
2 2 (or 7)-X substituted 5,10,15,20-tetraphenylporphyrin
H TPPPh R
2 4 4 2,7,12,17-Tetraphenyl-3,8,l3,18-R substituted porphyrin
[H TPP]
4
2+
5,10,15,20-Tetraphenylporphyrin diprotonated dication
HMPA Hexamethylphosphoramide
HOAc Acetic acid
HOMO Highest unoccupied molecular orbital
HR-MS High resolution mass spectrometry
Im Imidazole
z'-Pr z'-Propyl
LR-MS Low resolution mass spectrometry
LSIMS Liquid secondary ion mass spectrometry
LUMO Lowest unoccupied molecular orbital
m Meta
m Multiplet
MeCN Acetonitrile
l-Melm 1 (or N)-Methylimidazole
MeOH Methanol
(Me Si) NLi
3 2 lithium bis(trimethylsilyl)amide
rnin minute(s)
MnCTDCPP^O,),) P-Polynitro-5,10,15,20-tetalris(2,6-dicMorophenyl)porphyrinato
manganese(II)
MnfTDCPPCNO^Cl Chloro[P-polynitro-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]manganese(IH)
Mn(TE>CPP)Cl Chloro[5,l 0,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]manganese(III)
MnCTDCPPBr^Cl Chloro[2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tettakis(2,6-
dichlorophenyl)porphyrinato]manganese(III)
Mn(TDCPPF ) 8 2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinatomanganese(Ii)
Mn(TDCPPF )Cl 8 Chloro[2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]manganese(IH)
 XV

MnCTPFPPFg) 2,3,7,8,12,13,17,18-Octafluoro-5,l 0,15,20-

tettalds(perfluorophenyl)porphyrmatomanganese(ir)
Mn(TPPF ) 8 2,3,7,8,12,13,17,18-Octafluoro-5,l 0,15,20-
tetraphenylporphyrinatomanganese (II)
Mn(TPPF )Cl 8 Chloto(2,3,7,8,12,13,17,18-octafluoto-5,10,15^0-
tettaphenylporphyrinato)manganese(III)
MS Mass spectrometry
NADH Nicotinamide adenine dinucleotide
NADPH Nicotinamide adenine dinucleotide phosphate
N-alumina Neutral alumina
Ni(TPPBr ) 4 2,3,12,13,-Tetrabromo-5,10,15,20-
tetraphenylporphyrinatonickel(ir)
NBS N-Bromosuccinamide
NCS N-Chlorosuccinamide
NMP N-Methylpyrrolidone
NMR Nuclear Magnetic Resonance
0 Ortho
OAc Acetate
OEP 2,3,7,8,12,13,17,18-Octaethylporphyrin ligand
OETPP 2,3,7,8,12,13,17,18-Octaethyl-5,l 0,15,20-tetraphenylporphyrinato
ligand
ORTEP Oak Ridge thermal ellipsoid plot
OTf Triflate or trifluoromethanesulfonate
P Para
PFIB Perfluoroiodosylbenzene
PhCN Benzonitrile
PhIO Iodosylbenzene
Py Pyridine

pyrr-P-H pyrrolic P-protons

q Quartet
Rf (Distance moved by solute) / (distance moved by solvent front) in
TLC
r.t. Room temperature
s Singlet
SCE Saturated calomel electrode
T Temperature
TBABF 4 Tetrabutylammonium tetrafluoroborate
TBAP Tetrabutylammonium perchlorate
TBAPF 6 Tetrabutylammonium hexafluorophosphate
TCQ 2,3,5,6-Tetrachloroquinone
TEAP Tettaethylammonium perchlorate
Temp. Temperature
TFA Trifluoroacetic acid
THF Tetrahydrofuran
TLC. Thin layer chromatography
TPP 5,10,15,20-Tetraphenylporphyrinato ligand
UV Ultraviolet
 XVI

vdW van der Waals

ZnjTDCPPlNCg,) (3-Polynitro-5,10,15,20-tetrakis(2,6-
<dicUorophenyl)porphyrinatozinc(II)
Zn(TDCPP) 5,10,15,20-Tetrakis (2,6-dicUorophenyl)porphyrinatozinc(Ii)
Zn(TDCPPBr ) 8 2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinatozinc(II)
Zn(TPFPP) 5,10,15,20-Tettakis(perfluorophenyl)porphyrinatozinc(II)
Zn(TPFPPBr ) 8 2,3,7,8,12,13,17,18-Octabromo-5,l 0,15,20-
tettakis(perfluorophenyl)porphyrinatozinc(II)
ZnCTPPCCFj)^ P-Bis(ttifluoromemyl)-5,10,15,20-tetraphenylporphyrinatozinc(II)
ZnCrPP(CF )3(CF CF ))
3 2 3
7,8,17-Tris(trifluorornethyl)-l 8-pentafluoroediyl-5,l 0,15,20-
tettaphenylporphyrinatozinc(Ii)
Zn(rPP(CF )3)
3
7,8,17-Tris(trifluoromethyl)-5,l 0,15,20-
tettaphenylporphyrrnatozinc(Ii)
Zn(TPP(CF ) ) 3 4 2,3,12,13-Tetrakis(trifluoromethyl)-5,10,15,20-
tettaphenylporphyrinatozinc (II)
Zn(TPP) 5,10,15,20-Tettaphenylporphyrinatozinc(II)
Zn(TPPBr ) 4 2,3,12,13-Tettabromo-5,10,15,20-tetophenyporphyrinatozinc(II)
Zn(OMPTPP) 2,3,7,8,12,13,17,18-Octamethyl-5,l 0,15,20-
Tetraphenylporphyrinatozinc(II)
Zn(TPBC) 2,3,12,13-Tetrahydro-5,l 0,15,20-teteaphenylporphyrinatozinc(II)
or ^wo-tetraphenylbacteriochlorinzinc^i)
 XVII

NOMENCLATURE

The porphyrin core is a cyclic tetrapyrrolic system consisting of 20 carbons, four nitrogens,

and two hydrogens. Porphyrins are formally derived from porphin (I) by substitution of some or

all of the peripheral positions. The peripheral positions are numbered as shown in la and lb. Ia

follows I U P A C (International Union of Pure and Applied Chemistry) and IUB (International

I U P A C numbering system Fischer numbering system

Union of Biochemistry) nomenclature. 1 There is also an alternate system of nomenclature based

on the numbering system shown in lb which was developed by Hans Fischer.^ In modern

porphyrin chemistry, the former system of nomenclature (Ia) is adopted to name the large

number of synthetic and newly isolated porphyrins systematically. In IUPAC-IUB nomenclature

(Ia), positions 1,4,6,9,11,14,16,19 are termed the pyrrolic a-positions, 2,3,7,8,12,13,17,18 are the

pyrrolic P-positions and interpyrrolic methine positions 5,10,15,20 are /w.ro-posirions. For

example, compound II is named 5,10,15,20-tetraphenylporphyrin or wwo-teteaphenylporphyrin.

For the ligand name, porphyrin is changed to porphyrinato or porphinato as 5,10,15,20-

tetealds(2,6-dicMorophenyl)porphyrinatozinc(ir) (or meso-tettakis(2,6-

dichlorophenyl)porphyrinatozinc(ir;) (III). If the pyrrolic p-positions are partially substituted

 xviii

and no metal is coordinated to the porphyrin, the pyrrolic oc-carbon o f the pyrrole to w h i c h a

hydrogen attached is numbered first. F o r example, c o m p o u n d IV is 7,8,17,18-tetrabromo-

5,10,15,20-tetraphenylporphyrin (or 7,8,17,18-tefjrabromo-^j-o-tettaphenylporphyrin). When a

metal is coordinated, the pyrrolic a-carbon o f the pyrrole w i t h substituents o n the pyrrolic

P-position is numbered first as 2,3,12,13-tetramemyl-5,10,15,20-tettaphenylporphyrinatozinc(II)

(or 2,3,12,13-tetomemyl-^jo-tetraphenylporphyrinatozinc(l])) (V).

 XIX

ACKNOWLEDGEMENT

I would like to express my sincere gratitude to Professor David Dolphin for his guidance,

patience and encouragement throughout my entire research work. I also wish to take this

opportunity to thank members of Dolphin's lab for an enjoyable working environment. Special

thanks to Dr. Alison Thompson, Dr. Ethan Sternberg, and Dr. Elizabeth Cheu for proofreading

sections of this thesis. Especially, without Dr. Thompson's encouragement, I could not have

' continued my writing.

I would like to thank Professor Brian James for allowing me to use the cyclic voltammetry

apparatus in his lab. Thanks also to Dr. Ian Baird for showing me how to use the apparatus. I

also would like to thank Dr. Nick Burlinson for taking the time for his advice and helpful

discussions about N M R spectroscopy. Thanks also to Ms. Marietta Austria and Ms. Liane Darge

for taking nice N M R spectra and for teaching me how to use the N M R machines, to Mr. Peter

Borda in the microanalysis lab, Drs. Steve Rettig and Brian Patrick in the X-ray crystallography

lab, staff in the Mass Spectrometry lab for their technical support, and to Mr. Brian Ditchburn in

the glass shop for making the electrochemical cell.

Thanks also to those people, over the years, who made it an enjoyable experience for me

to work in the department of Chemistry at U B C . Special thanks to Dr. Yoshikata Koga for his

encouragement and to Drs. Alavi Saman and Mari Kono for their friendship and memorable

time in Vancouver. I am also very grateful to Professor Akinori Jyo at Kumamoto University,

Japan, who introduced to me a fascinating realm of chemistry.

Last, I would like to thank my wife Miyuki whose smile and patience were essential to

completion of this thesis.

 1

CHAPT
E RI

Introduction

A. I
n t
roduct
i
o n

Hemoproteins perform vital functions in nature. These include molecular oxygen

transport and storage-^, electron transfer^, molecular oxygen activation^, a n c j the

metabolism of organic intermediates. 10-12 "T^Q prosthetic group for most hemoproteins is the

protoporphyrin IX Fe complex (Figure 1-1), despite the varying functions of this family of

proteins. 13,14 ' p j presence of the protoporporphyrin I X skeleton within various hemoproteins
ie

of different function is intriguing and many model studies using synthetic porphyrins have been

performed in attempts to identify the mechanism of action of hemoproteins.

Figure 1-1. Protoporphyrin I X Fe complex.

Synthetic porphyrins used in model studies of hemoproteins have been prepared using

design strategies involving both structural and electronic modifications. Early examples of

structurally modified porphyrins used in the model studies of hemoglobins and myoglobins

include sterically hindered derivatives!5-17 w n ii e recent examples have explored non-planar

derivatives.!8-20 s m d y of nonplanar porphyrins is motivated by the hypothesis that fine-

tuning of the porphyrin macrocycle conformation by the protein scaffold of hemoproteins is one

way that nature might use to control the functions of prosthetic groups in tetrapyrrole-protein

complexes. 18,19,21 -24

Electronically modified porphyrins incorporating strong electron-withdrawing substituents

form a class called "electron-deficient porphyrins" (Figure 1-2). Strictly speaking, the term

"electron-deficient" refers to compounds for which full octets are not achieved in the Lewis

R 2
R 1
R 2

R = Aryl, C F
1
n 2 n + 1

R = F, CI, Br, N 0
2
2

M = 2 H , Zn(II), Fe(III)Cl, Mn(IU)Cl

+

R 2
R 1
R 2

Figure 1-2. Examples of electron-deficient porphyrins.

structure25 (e.g. B H ) . However, the term is arbitrarily used in the literature to refer to
2 6

porphyrins in which the electron density of the macrocycle has been lowered by the presence of

strong electton-withdrawing substituents. Many electron-deficient porphyrins have been

reported, largely as a result of studies directed towards the determination of the ability of their

metal complexes (such as Cr(III), Mn(III), or Fe(III)) to mimic cytochrome P-450.26-28

Cytochrome P-450 enzymes include the protoporphyrin LX Fe(III) complex and are responsible

for O z activation and oxygen atom transfer (oxygenation) in substrates witiiin biological

systems.^
 Biological oxygenation has attracted much attention because the biological systems

perform selective oxidation under mild reaction conditions using the abundant oxidant 0 2 and

release water only as a by-product.13,14 Besides P-450, enzymes methane monooxygenase and

copper oxygenases such as phenylalanine hydroxylases or tyrosinase are also known as enzymes

that catalyze oxygen transfer in substrates utilizing O and model studies have been continued in
z

order to understand the mechanisms of the enzymes. 13,14 Elucidation of the mechanisms may

potentially aid in the development of useful transition metal catalysts for both fundamental and

industrial chemistry.

In fundamental developments some potentially useful metal complexes that are not

derived from biological systems have also been introduced and studied as oxidation catalysts.29

The most successful examples are Mn(III) complexes of derivatives of salen (Figure 1-3).^,31

The catalytic system with the complexes formed the basis for the development in asymmetric

catalytic epoxidation using iodosylbenzene or N a O C l . In industry, some important organic

intermediates have been synthesized by catalytic oxidation. For example, oxidation of ethylene to

ethylene oxide using A g O or propene to acrolein using B i M o O as the catalysts is the worldwide
2 e

known oxidation processes.32

F i g u r e 1-3. Example of salen Mn(III) complex

 4

Oxidation by biological systems is much more sophisticated than such industrial processes

in terms of the range of the substrates and the reaction conditions. 13,14 In spite of these

advantages, porphyrins have not been used in industry, although potential commercial

applications of some of the metalloporphyrin systems have been shown.^3 The major reasons

for this are probably cosdy preparation and instability of the metalloporphyrins in catalytic

oxidations. However, successful development of a system potentially derived from biological

systems such as P-450 is still in strong demand for fine, economical, and environmentally

friendly chernistry.26,29 Thus, porphyrins have been the major subject in catalytic oxidations for

years. In particular, electron-deficiency has been thought to be essential for mimics for P-450

enzymes in order to acquire efficiency and robustness of catalysts34-48 a n c j fae se a r c h for a

"perfect" P-450 mimic continues, as described in chapter I of this thesis.

This thesis documents the synthesis and investigation of the properties of some novel

electron-deficient porphyrins. In particular, the design, synthesis and electronic properties of

p-trifluoromethyl-«?^o-tetraphenylporphyrins will be discussed, in relation to their potential

application as cytochrome P-450 rnirnics.

The first part of Chapter I is a review of the development of electron-deficient porphyrins

as P-450 mimics, followed by the discussion of design strategies employed for the preparation of

novel P-tafluoromediy-^j-o-tetraphenylporphyrins. The remaining part of this chapter is a

review of the various analytical methods applicable for the characterization of porphyrins and the

evaluation of electron deficiency within the porphyrinogenic macrocycle.

 5

B . Metalloporphyrins as cytochrome P-450 model compounds

/. Cytochromes P-450

a. Distribution, nomenclature, and structure

Cytochromes P-450 (P-450s) are intercellular proteins w i t h molecular weights between 50

and 60 k D . ' > ^ They contain protoporphyrin I X Fe(III) complex (often called "heme") as the

prosthetic group.' P-450s are widely distributed i n nature from bacteria to mammals.'

It was found that reduction o f the Fe(III) form o f a P-450 enzyme to its Fe(II) state,

followed by coordination o f carbon m o n o x i d e results i n the formation o f an intense absorption

band w i t h a m a x i m u m at about 450 n m i n the optical spectrum.49 T h i s p h e n o m e n o n led

O m u r a and Sato to name this type o f substance P-450 (a pigment that absorbs light at

450 n m ) - 4 9

Tyrosine

Phenylalanine

Cysteine

F i g u r e 1-4. A c t i v e site and h y d r o p h o b i c pocket o f cytochrome P - 4 5 0 .

cam

D a r k atoms show hydrogen b o n d i n g (a), h y d r o p h o b i c interaction (b), and

coordination sphere o f the heme (c). A d a p t e d f r o m reference 13.
 To date, several P-450 structures are known and it has been shown that all

stmcture-determined P-450s share a common protein fold.50 Thus, the heme is buried in the

hydrophobic pocket of the protein structure and is coordinated to the thiolate ligand of a

terminal cysteine moiety.^, 14,50 The heme-thiolate ligand environment is highly conserved in

all P-450s, whatever the exact function of particular enzymes.^ Figure 1-4 shows the X-ray

crystal structure of the active site of camphor bound cytochrome P-450 .51
cam The

protoporphyrin IX Fe(III) complex, the axial thiolate ligand, and the bound camphor as a

substrate can been seen within this protein structure.

b. Function and mode of action

P-450s play an essential role in the metabolism of endogenous substances (e.g. steroids)

and in the detoxification and degradation of substances in animals, plants, and bacteria. 13,14

P-450s catalyze the oxidation of organic substrates by molecular oxygen in cooperation with

reducing agents ( N A D H , flavoprotein and iron-sulfur proteins). 14 As shown in equation (1.1a),

alkanes are oxidized to alcohols^ and alkenes are oxidized to epoxides (1.1b), by action of P-450

catalysis. Similar catalysis is effected by synthetic Fe(III) and Mn(III) porphyrins. ^3

RCH -H 2 + 0 2 + 2 H + 2e"
+
• RCH -OH
2 + H 02 (l.la)

X> (!' )
lb

Figure 1-5 shows the currendy accepted mode of action of P-450s.l3>14 ca talyti c

cycle is initiated by incorporation of a substrate molecule (RH) into the hydrophobic pocket of

the protein where the heme-thiolate complex is located. This is accompanied by concomitant

loss of a water molecule from the hexa-coordinate Fe(III) complex (T). This step results in a
 = [protoporphyrin IX] '
2

S"-Cys

Figure 1-5. Catalytic cycle of cytochrome P-450.

 8

penta-coordinate complex (2) w i t h high-spin Fe(III). A n electron donated by N A D P H is

transferred to the complex via electron-transfer systems such as flavoprotein or iron-sulfur

proteins and reduces (2) to the high-spin penta-coordinate Fe(II) complex (3). T h i s complex

subsequendy binds 0 2 to f o r m the low-spin oxy Fe(II) complex (4). T h e F e ( I I ) / 0 moiety is

2

possibly modified to F e ( I I I ) / 0 2 i n (5). T h e one-electron reduction o f (5) forms the low-spin

peroxo Fe(III) complex (6). T w o protons add to this species and one molecule o f water is

released. T h u s cleavage o f the O - O b o n d results i n the o x o Fe(rV) porphyrin cation radical (7),

w h i c h reacts w i t h the hydrocarbon substrate to yield an alcohol (or an epoxide w h e n an olefin is

incorporated). T h e heme returns to the resting f o r m (1) after the coordination o f water. A s

indicated i n Figure 1-5, the cycle can be bypassed (via a "shunt path") by adding oxygen

donors ( X - O ) such as iodosylbenzene. Since P-450s can catalyze the cleavage o f strong C - H

bonds i n hydrocarbons (e.g. 400 k j / m o l for cyclohexane)54 under ambient conditions, chemists

have been intrigued to m i m i c the remarkable function o f these enzymes using synthetic

metalloporphyrins. It should be noted that n o simple (i.e., non-enzyme) complex o f Fe(III) has

been described w h i c h really can use /-alkyl hydroperoxides to m i m i c a monooxygenase (i.e.,

P-450 like) catalyzed oxidation o f alkanes.55

c. Mechanisms of hydrocarbon oxidation

(1) Mechanism of alkane hydroxylation

Figure 1-6 shows a general scheme for the cytochrome P-450 catalyzed hydroxylation o f

alkanes. A s discussed i n the previous section, the o x o Fe(IV) p o r p h y r i n cation radical is the

active species. T h e mechanism is considered to occur first by hydrogen atom abstraction f r o m

the substrate followed by rapid transformation o f the metal-bound hydroxy radical to an

intermediate alkyl radical. T h e n combination o f the hydroxy radical w i t h alkyl radical forms the

alcohol and the porphyrin returns to the resting s t a t e d F o r m a t i o n o f the side product is also

s h o w n i n Figure 1-6; escape o f the alkyl radical from the cage o f the transition state, initiates a

radical chain autoxidation that produces ketone.56

O *R
/ - T l <* R
" H
,H
Fe(lll)J) + R O H
alcohol

escape
•R -•ROO*

O, t
= porphyrin 71 cation radical

R-H = alkane
ketone

Fi
g ur
e 1-6. M e c h a n i s m o f alkane hydroxylation by cytochrome P-450.

(2) Mechanism of alkene epoxidation

Mechanisms for epoxidation by P-450s are more complicated than that for

hydroxylation.53,57 Figure 1-7 (p. 10) shows a unified mechanism for the epoxidation o f olefins

by cytochrome P-450 summarized from the literature.58~61 Firstly, the charge transfer

complex (1) is formed. This complex then collapses to the carbocation complex (2) by

electrophilic addition o f the oxo Fe(rV) porphyrin 71-cation radical to the olefin. R i n g closure o f

(2) forms the epoxide (3) and Fe(III) porphyrin. Several side products are also formed. H y d r i d e

and group migration results i n the aldehyde (4) and the ketone (5) respectively. In each side-

reaction Fe(III) porphyrin is generated. N - A l k y l a t i o n to give (6) and iron-carbon bond

formation to give (7) can also occur. A l t h o u g h the major product is always the epoxide (3), the
 10

extent of each of the alternative pathways depends on the individual porphyrins and

substrates.53 ^ R R R R
R
+
o 6 o

R R
epoxidation

O
R
R

H migration R R
• o
Fe(lll) O

-+ R R
R migration O

F e - C bond formation
R

Fi
g ur
e 1-7. Mechanism of the oxidation of olefins by cytochrome P-450
or metalloporphyrins.
 11

2. Synthetic metalloporphyrins as P-450 mimics

a. Structures ofporphyrins that appear in this section

In order to proceed, the major porphyrins that appear i n section B.2.b are shown i n

Figure 1-8. Section B.2.b. documents the investigation of synthetic porphyrins and

metalloporphyrins as P-450 mimics.

Porphyrin R i r )
R 2

M(TPP) (2) phenyl H

M(TMP) (3) mesityl H
M(TPFPP) (4) perfluorophenyl H
M(TDCPP) (5) 2,6-dichlorophenyl H
M(TPCPP) (6) perchlorophenyl H
MfrPPBrg) (7) phenyl Br
M(TPFPPBrg) (8) perfluorophenyl Br
MfTDCPPBrg) (9) 2,6-dichlorophenyl Br
MfTDCPPCL) (10) 2,6-dichlorophenyl CI
M(TPCPPC1 ) 8 (11) perchlorophenyl CI
M(TPPF ) 8 (12) phenyl F
M(TDCPPF ) 8 (13) 2,6-dichlorophenyl F
MCTPFPPFs) (14) perfluorophenyl F
MCTDCPPCNO^flS) 2,6-dichlorophenyl N0 2 or H
M(C Fn) P (16)
7 n + 1 4
C F H
^ n 2n+l
1

(a) M = 2 H ; (b) M = Zn(II); (c) M = C u ( H ) ;

(d) M = Fe(III)Cl; (e) M = Fe(II); (f) M = M n ( I I I ) C l ;
(g) M = Mn(II)

** Catalogue for R aryl groups 1

R 1
R 3
R 4
R 5

phenyl H H H
Pmeso mesityl CH 3 H CH 3

perfluorophenyl F F F
2,6-dichlorophenyl CI H H
perchlorophenyl CI CI CI
PmeSO'. meso-rposixion
o f porphyrin

Figure 1-8. Porphyrins used i n P-450 m o d e l studies.

 12

b. Synthetic methodsfor the majorplayers in the early development of PA 50 mimics

(1) Condensation of pyrrole with arylaldehydes

Porphyrins used in early P-450 model studies were symmetric and easy to prepare,-^ via

the condensation of equimolar quantities of pyrrole (or a 3,4-disubstituted pyrrole) and an

arylaldehyde, followed by oxidation. 62-67

This strategy was originally used by Rothmund, who reacted pyrrole and benzaldehyde in

pyridine in a sealed flask at 150 °C for 24 h to yield «?MO-tetraphenylporphyrin (H TPP) (2a) in

2

about 3% yield.°2 The yield was improved up to 40 % by Adler, Longo and coworkers who

carried out the reaction in propionic acid or acetic acid open to the air (Scheme 1-1

Path y4).63,64 Reasoning that porphyrin is formed via the formation of porphyrinogen (17)65,

o N
C
II
Path/*
Propionic or
O
acetic acid/air

Path B

H +

S
che
m e 1-1. Synthesis of wwo-tetraarylporphyrins.

Lindsey et al. revised the method devised by Rothmund, and Adler-Longo.66 The Iindsey

method (Scheme 1-1 Path 13)66 j s a two-step one-pot procedure whereby the pyrrole and the
 13

aldehyde are condensed with a catalytic amount of acid under anaerobic conditions to form

porphyrinogen, which is subsequently oxidized to porphyrin by an oxidant such as 2,3,5,6-

tetrachloro-quinone (TCQ) or 2,3-clicMoro-5,6-dicyano-quinone (DDQ). The initial reaction is

carried out in a chlorinated solvent such as C H C 1 or CHC1 at room temperature for about 1 h
2 2 3

before the oxidant is added. One drawback relating to this method is the rather low reaction

concentrations (as low as 10" M ) . 2 6 6

However, the mild reaction conditions of this method have

allowed the synthesis of WOT-tetramesitylporphyrin (H TMP) (3a),2 «?&ro-tetrakis-

(perfluorophenyl)porphyrin (H TPFPP) (4a), 2 ^j-o-tetralds(2,6-dicruorophenyl)porphyrin

( H T D C P P ) (5a), and OTWo-tettaltis(perchlorophenyl)porphyrin (H TPCPP) (6a) (see Figure 1-8,

2 2

p. 11)67 w n 0 s e syntheses and isolation had not been possible by the Rothmund or Adler-Longo

methods. - 63 64

Metallation of porphyrins to give metalloporphyrins is generally achieved by the reaction

of porphyrin with a metal salt under various conditions. ^> ^ Thus, access to Fe(III) or Mn(III)
6 6

complexes of porphyrins 2-6 that were important for P-450 model studies became possible.

(2) /3-Perchlorinated andperbrominated meso-arylporphyrins

(3-Octachloro and P-octabromo-tettaarylporphyrins cannot be synthesized by

condensation of 3,4-dichloro- or 3,4-dibromopyrrole and aryl aldehydes due to the difficulty

incurred in preparation of the requisite 3,4-dihalopyrroles.^^ Direct chlorination and

bromination of the P-pyrrolic positions of porphyrins have been reported to be extremely

efficient to effect structural and electronic modifications of tetta-arylporphyrins (Scheme 1-2).^0

p-Chlorination^l ^ and bromination ,44,71,75-77

- 4 34
D f metallated porphyrins can be achieved

using various cMorinating (Cl , N-chlorosuccinamide

2 (NCS)) and brominating (Br ,
2
 14

N-bromosuccinamide (NBS)) reagents in numerous solvents (CHC1 , CC1 , C H C 1 and MeOH).

3 4 2 2 4

Metallation of porphyrins prior to this reaction is necessary in order to complete

P-halogenation.^O As shown in Table 1-1, yields for P-halogenation are generally high. Due to

the ease of synthesis, and their unique characteristics, halogenated porphyrins have been

extensively studied as P-450 mimics.

X = Br and CI

Sch em e 1-2. P-Halogenation of OTWo-tetraarylporphyrin. A r = phenyl, mesityl,

perfluorophenyl, 2,6-dichlorophenyl, perchlorophenyl, M = Ni(II), Cu(II), Zn(II),
Mn(III)Cl and Fe(III)Cl.

Tabl
e 1-1. Yields of typical P-perhalogenation reactions.
Starting porphyrin P-halogenated Yield (%) Reference
Cu(TPP) (2c) Cu(TPPBr ) 8 (7c) 75 75
Zn(TPFPP) (4b) Zn(TPFPPBr ) 8 (8b) 60-80 78
Zn(TDCPP) (5b) Zn(TDCPPBr ) 8 (9b) 71 34
Fe(TPCPP)Cl (6d) Fe(TPCPPCl )Cl 8 (lid) 85 73

c. Early development of P-450 mimics

In 1979 Groves et al. investigated the oxidation of several hydrocarbons using a synthetic

porphyrin, Fe(TPP)Cl (2d) (Figure 1-8, p.11), as catalyst and iodosylbenzene (PhIO) as oxidant
 15

and demonstrated the P-450-like catalytic activity of the metalloporphyrin via a "shunt path"

mechanism.79 For example, cyclohexene and cyclohexane were converted into cyclohexene

oxide (55 %) and cyclohexanol (8 %) respectively.^ This original work pioneered model studies

towards the investigation of other metal complexes of T P P (such as 1^(111)80,81^ Cr(III)82 5 Q r

Ru(VI)83) the effect of basic axial ligands84-87 the effect of oxygen donors88-91
) ; 5 a n c j u s e Q f 0 2

as oxidant in the presence of a coreductant (such as N a B H or Zn(Hg) for Fe(III/II) reduction

4

to mimic the natural P-450 oxidation process.92-95 Although the TPP-based catalysts (first-

generation catalysts) were relatively effective mimics of P-450 reactions, there was a problem in

that their catalytic activity was rapidly decreased by oxidative degradation of the

metalloporphyrins.26-28 Since the oxidative degradation of metalloporphyrins is known to

occur readily at the meso ring p o s i t i o n ^ ^ ^ protection of this position became an important goal

for the improvement of catalytic activity. Two approaches were developed for the protection of

the ^jo-positions; protection of the meso-X50%\Xuor\s> from the oxidant by bulky adjacent groups-^

and the introduction of strong electton-withdrawing groups, which is also important to obtain an

active metal center.99

Groves et al. showed that Fe(TMP)Cl (3d) (Figure 1-8, p.11) can resist, to some extent,

oxidative degradation due to the steric effect of bulky mesityl groups at the wwo-positions.98

Also, Chang and Ebina carried out the epoxidation of cyclohexene with an electron-deficient,

Fe(TPFPP)Cl (4d) (Figure 1-8) and PhIO as oxidant and obtained cyclohexene oxide in 95 %

yield.99 When both steric bulk at the Wcvo-positions and electton-withdrawing groups are

combined witiiin a wwo-arylporphyrin, catalytic behavior is improved tremendously. In 1984,

Traylor et al. reported a turnover (mole of product/mole of catalyst) of 10,000 and 85 % yield in
 16

the epoxidation of norbornene using Fe(TDCPP)Cl (5d) (Figure 1-8) and

pentafluoroiodosylbenzene (PFIB) as oxidant. These improved metalloporphyrins, 3d, 4d,

and 5d, are called second-generation catalysts.26,28

Although the second-generation catalysts effectively catalyze the epoxidation of alkenes,

the oxidative degradation of these Fe(III) porphyrins is still noticeably severe during alkane

hydroxylation.28 J N a n attempt to synthesize more robust catalysts, perhalogenation at the

p-pyrrolic positions was performed to give third-generation catalysts. The first third-generation

catalyst, Fe(TDCPPBr )Cl (9d) (Figure 1-8) was reported by Traylor and Tsuchiya in 1987.
8
34
In

1990, three more third-generation catalysts, FeCTPFPPBr^Cl (8d) (Figure 1-8),

44

Fe(TDCPPCl )Cl(10d) (Figurel-8) and FeCTPCPPCkJCl (lid) (Figure 1-8) were reported.
8
73 73

These metalloporphyrins are much more electron-deficient compared to the first and the second

generations, as a result of P-Br and CI substituents. This can be appreciated by consideration of

the Fe(III/II) redox potentials of the iron porphyrins. For example, the Fe(III/II) redox

potential of l i d is positively shifted by 0.64 V from that of Fe(TPP)Cl (2d) (Figure 1-8). 73
The

effects of electron-withdrawing substituents were further investigated due to the ready synthesis

of these highly electron-deficient porphyrins (section B.2.a.(2). in this chapter) and resulting

increase in catalytic activity.26-28

d. Electron-withdrawing effects on catalytic activities

Before we move into this subject, we should keep in mind that investigations of catalytic

oxidation are normally conducted in the presence of excess substrate. Therefore, for example,

oxidation of alkane is forced to cease at the formation of alcohol, and alcohol to ketone by

catalysis is not a competing reaction. We should also keep in mind that the detailed reaction
 17

conditions such as reaction media, mole ratio of reactants, or oxidants are different from one

report to another, which makes direct comparison of product yields between different

experiments very difficult. Thus, the comparison of the catalysts should be done within

experiments performed under the same conditions.

Traylor et al. studied the hydroxylation of cyclohexane and norbornane using

Fe(TDCPPBr )Cl (9d)

8 (Figure 1-8) and PFIB as oxidant. 101 The yield of cyclohexanol was

93% based on the consumed PFIB with a high ratio of alcohol to ketone (37/1). The

hydroxylation of cyclohexane using Fe(TPP)Cl (2d) (Figure 1-8) and PhIO gave an alcohol to

ketone ratio of 12/1.52 As explained in section B.l.c.(l)., formation of the ketone side product

results from the escape of the alkyl radical from the cage of the transition state.-^ In other

words, the oxo Fe(TV) porphyrin 7t-cation radical obtained from electron-deficient 9d is more

reactive than that formed from 2d and thus gives the alkyl radical less opportunity to escape

from the cage. 101 The hydroxylation of norbornane with 9d and PFIB gave the corresponding

alcohol in 82 % yield with much higher selectivity for alcohol (alcohol to ketone > 99/1).101

Traylor et al. also investigated the reactivity of the oxo Fe(rV) porphyrin 7t-cation radical towards

the bond cleavage of / - B u O O - H and alkene epoxidation (Figure 1-9). 102,103 j t l s necessary to

prevent the side reaction (Path B) in order to obtain a high yield of epoxide (Path A) using

A B u O O H as an oxygen donor (Figure 1-9). The value o£k /k ,A B where k = rate of epoxidation
A

and k = rate of /-BuOO' formation, indicates selectivity for the epoxidation (Path A). When
B

Fe(TMP)Cl (3d) (Figure 1-8) was used as a catalyst, k /kA B = 0.01 for cyclic alkenes

andABuOOH, while k /k A B > 1 with Fe(TPFPP)Cl (4d) (Figure 1-8) and F e f T D C P P B r ^ C l (9d)
 18

(Figure 1-8) as the strength of the electron-withclrawing substituents was increased. 103

M o r e o v e r , the rate o f metalloporphyrin destruction was also decreased. 102

(Path A)
alkene
epoxide
CI O
\ PPIR
QFe(lll)J) >• ( Fe(IV)
(Path S)
f-BuOOH
7^) = porphyrin dianion f-BuOO •

i-a

= porphyrin 71-cation radical

Figure 1-9. R e a c t i o n o f o x o F e ( I V ) p o r p h y r i n 7t-cation radical w i t h alkene and

^-BuOOH.

Bartoli et al. compared the effectiveness o f Fe(III) porphyrin catalysts (5d and lOd)

(Figure 1-8) i n the hydroxylation o f heptane using P h I O . 4 0 T h e total yields (heptanols +

heptanones) by 5d, and lOd were 36 and 80 % , respectively. T h e regioselectivities for the

position o f hydroxylation (2, 3, and 4 positions o f heptane) were 58:30:12 (positions 2:3:4) for 5d

and 43:40:16 for lOd. H i g h e r reactivity o f the o x o Fe(TV) p o r p h y r i n 7T.-cation radical o f the more

electron-deficient metalloporphyrin 10b leads to lower regioselectivity of hydroxylation.

Carrier et al. showed that hydroxylation o f anisole w i t h M n ( T D C P P ) C l (5f) (Figure 1-8) and

H O
2 z as an oxygen d o n o r gives ^wra-hydroxyanisole w i t h 95 % regioselectivity and i n 50 % yield,

while w i t h M n ( T D C P P B r ) C l (91) (Figure 1-8) 75 % regioselectivity occurs and 70 % yield o f

8

hydroxyanisole obtained.^ 0
These results can similarly be explained by the higher reactivity o f

the third-generation catalyst 9f compared to the more electron rich 5f.

Ellis and L y o n s reported the oxidation o f isobutane using Fe(III) porphyrins and

molecular oxygen without the requirement for a coreductant.44,45 F e ( T P F P P B r ) C l (8d)

8

(Figure 1-8) catalyzed the oxidation o f isobutane to /-butanol more efficiently than the second-
 19

generation catalyst F e ( T P F P P ) C l (4d) (Figure 1-8) i n terms o f the product yield and

turnover.44,45 - p h e u s e Q f resulted i n the formation o f Abutanol w i t h greater than 90 %

selectivity a n d a total turnover o f 12,000. T h e catalytic activity o f 8d was maintained for 74 h .

Table 1-2 shows the Fe(III)/(H) redox potentials and catalytic activities (turnovers) observed for

the oxidation o f isobutane w i t h Fe(III) porphyrins o f different generations, a n d electronic

properties, under identical condition.45 Electron-deficiency is reflected b y the positively shifted

Fe(Iir)/(II) redox potentials o f the second and the third-generation catalysts, (4d and 8d)

respectively. It was believed that catalytic activity could be mapped b y an increase o f the

Fe(III)/ (II) redox potentials, highlighting the inherent relationship between electron-deficiency

and catalytic activity o f the metaUoporphyrin.45

Tabl
e 1-2. Relationship between catalyst i r o n redox potentials
and activities/
Total
Catalyst Fe(III)/(II),E 1/2 (V) b

turnovers 0

Fe(rPP)Cl (2d) -0.221 0

F e ( T P F P P ) C l (4d) +0.07 1160
F e C T P F P P B r ^ C l (8d) +0.19 1800
a
Ref.45. C y c l i c voltammetry i n C H C 1 vs. S C E . Supporting electrolyte;
b
2 2

tetrabutylammonium perchlorate ( T B A P ) .
c
M o l e o f p r o d u c t / m o l e o f catalyst for the oxidation o f isobutane i n benzene at 60°C.

Ellis and L y o n s proposed a mechanism to rationalize the oxidation o f isobutane by the

catalyst a n d 0 2 alone (Figure 1-10).44,45 ' p i u s mechanism includes three key assumptions; (i) due

to the positively shifted i r o n redox potential, Fe(II) is produced by homolytic cleavage o f

F e ( f f l ) - C l (1), (ii) after the successful binding o f 0 2 to give (2), formation o f the

u—peroxodimer (3) a n d then the catalytically active o x o Fe(TV) p o r p h y r i n (4) occurs w h i c h then

oxidizes the substrate, via H abstraction and a ' O H rebound mechanism (6), (iii) due to the bulky
 20

Figu re 1-10. Catalytic cycle for isobutane hydroxylation by 0 2 and 8d proposed

by Ellis and Lyons. Reference 44 and 45.
 21

and severely distorted porphyrin structure, formation of the ^-oxodimer (5), which is catalytically

inactive^ 04,105^ i suppressed. The experimental data obtained, and the mechanism described by
s

Ellis and Lyons, was extremely interesting since it involves the least expensive oxygen atom

source, 0 , as the oxidant. 106

2

In fact, subsequent studies revealed that Fe^TPFPPBrg) (8e) (Figure 1-8) is extremely

stable and binding of oxygen to this species is unlikely. 104,107 Grinstaff etal.^^ showed that an

alternative radical-chain autoxidation mechanism is operative in the experiments carried out by

Ellis and Lyons.44 Additionally, Bottcher et al. showed that molecular modeling based on a

radical-chain autoxidation mechanism fit well with the catalytic activities of 8d (Figure 1-8) in

alkane hydroxylation using O .104 The role of 8d in a radical-autoxidation mechanism was

2

thought to involve the decomposition of alkyl hydroperoxide. 104,107 j n o m e r words, electron-

deficient porphyrin 8d is a very efficient catalyst for hydroperoxide decomposition and,

therefore, oxidation.

In summary, metalloporphyrins substituted with bulky and/or electron-withdrawing

substituents are much more efficient and robust catalyst than unsubstituted metalloporphyrins.

Investigations regarding the relationship between electron-deficiency and catalytic activity or

robustness is still an active area in P-450 mimic research.42,43,47,48 The next section of this

thesis will further discuss the effects of the introduction of electron-witlidrawing substituents

onto the periphery of metalloporphyrin macrocycles.

 22

e. Newer generation of electron-deficient porphyrins

(1) (5-Verfluoro-meso-tetraarylporphyrins

(a) Synthesis

Direct fluorination of Zn(TPFPP) (4b) (Figure 1-8) using C o F 3 or A g F in C H C 1

2 2 was

reported in 1989^8 D U t this method has not been utilized by others because it is

itreproducible.28 Recent successful synthesis of 3,4-difluoropyrrolel09 has enabled the

synthesis of (3-octafluoro-tetraarylporphyrins (12-14) (Figure 1-8) by condensation of the 3,4-

difluoropyrrole and aryl aldehydes. - 36 41

> 43
Metallation using Mn(II) gave M n f T P P F ^ C l (12i),

Mn(TPPF ) (12g),
8 M n C T D C P P F ^ C l (13f), and MnfTDCPPFg) (13g). MnfTPFPPFg) (14g)

(Figure 1-8) was the only manganese species obtainable for 14 due to the strong electron-

withdrawing effect of the substituents. Normally Mn(III) is the most stable oxidation state in M n

porphyrin chemistry but Mn(II) porphyrin can be isolated as a stable compound due to the high

electron-deficiency of porphyrin ligands 13 and 1 4 . 43

Fe(III) porphyrins of 12-14 were also

synthesized. ^4

(b) R o b u s t n e s s test

Porhiel et al. evaluated the robustness of iron and manganese complexes towards oxidative

degradation of 12-14 by observing the decrease in Soret absorption (see section D.l.a. for a

description of the use of UV-vis absorption spectroscopy for the study of porphyrins and

metalloporphyrins) in the presence of oxidants PhIO and H 0 in the absence of substrate . 42,4-3
2 2

Oxidative degradation of the metalloporphyrins would inevitably result in a decrease in the

intensities of the UV-visible absorption band. Thus, UV-visible spectroscopy provides an ideal

method for determination of the robustness to oxidation of the potential catalysts.

 23

FeCTPPFgJCl (12d), F e f T D C P P F ^ C l (13d) and FefTPFPPF^Cl (14d) (Figure 1-8) were

less stable to oxidation than the second-generation catalysts Fe(TPFPP)Cl (4d) and

Fe(TDCPP)Cl (5d) (Figure l-8).42 Interestingly, 14d, which is the most electron-deficient

species based on the porphyrin ring redox potential of zinc derivatives (the first ring oxidation

potential for ZnfTPFPPFg) (14b) (Figure 1-8), 1.70 V vs. S C E ; for Zn(TPP) (2b) (Figure 1-8),

0.80 V vs. S C E in C H C 1 ) 6 2 2
3
; w a s the least robust towards oxidative degradation when

comparing 12d-14d, 4d, and 5d.42 The manganese complexes Mn(TPPF )Cl (121),
8

Mn(TPPF ) (12g),
8 MntTDCPPF^Cl (13f), Mn(TDCPPF ) 8 (13g) and Mn(TPFPPF ) (14g) g

(Figure 1-8) with PhIO as oxidant showed similar stability towards oxdative degradation to that

of Mn(TPFPP)Cl (4f) and Mn(TDCPP)Cl (5f) (Figure 1-8). With H 0 2 2 as oxidant, 12f, g and

13f, g were less stable than 2f, 4f and 5f. Metalloporphyrin 14g remained as the Mn(II) species

even in the presence of H 0 , suffering no oxidation.42

2 2

It is reasonable to expect that a higher ring oxidation potential of a porphyrin ligand would

be advantageous to increase the stability of the porphyrin catalyst to oxidation but these results

suggest that the presence of strong electron-withdrawing groups is not always accompanied by

robustness and high activity of the corresponding catalyst.

(c) O x i d a t i o n studies

Hydroxylation of cyclohexane and epoxidation of cyclooctene with iron complexes

12d - 14d and PhIO in C H C 1 gave similar results to those found using 4d and 5d as catalysts ie
2 2

10-30 turnovers/1.5 h for both substrates. However, the oxidation of cyclooctene with 12d —

14d and H 0 2 2 was found to be less successful (3-4 turnovers) than with 4d and 5d (10-60

turnovers).42 These results concur with the results of the robustness test. Interestingly, 14d was
 24

the only c o m p o u n d that catalyzed the hydroxylation o f benzene to phenol, w h i c h is more

difficult than hydroxylation o f an alkane i n terms o f the C - H b o n d cleavage ( C - H b o n d energy is

400 k j / m o i for cyclohexane and 464 k j / m o l for b e n z e n e ) ^ w i t h 2 turnovers i n the presence o f

H 0 . 4 2 T h i s may i m p l y that the oxo Fe(TV) porphyrin 7t-cation radical formed from 14d is
2 2

reactive towards the strong C - H b o n d o f benzene, but oxidative destruction o f itself is extremely

competitive due to its high reactivity.

Cyclohexane oxidation w i t h manganese complexes 13f, g and 14g, w h i c h feature b o t h

electton-withdrawing groups at the /#£fo-positions and electron-withdrawing fluorine substituents

at all o f the P-positions, and P h I O i n C H C 1 2 2 resulted i n 10 - 30 % yield (cyclohexanol +

cyclohexanone). There was little improvement from the oxidation o f cyclohexane w i t h 4f and 5f,

w h i c h do not have P-substituents. T h e oxidation o f cyclooctene w i t h 13f, g and 14g and H 0 2 2 in

C H C 1 / C H C N ( 1 / 1 ) d i d not give epoxide, while 4f and 5f yielded epoxide i n 69 % and >98 % ,

2 2 3

respectively.

(d) C o n c l u s i o n

F r o m the results shown above, P o r h i e l et al. concluded that instability towards oxidative

degradation and l o w catalytic activities o f p-octafluoro-wwo-tettarylporphyrins might arise from

the combination of catalyst susceptibility to nucleophilic attack, potential oxidative

decomposition o f the metal o x o species, and extremely stable l o w oxidation metal state (e.g.

Mn(ir)).42,43 Evidently, the introduction o f strong and plentiful electton-withdrawing groups

per se does not result i n effective P-450 m i m i c catalysts.

 25

(2) B-Nitro-meso4etrakis(2,6-dichlorophenyl)porphyrins

(a) Synthesis

Ozette et al. have reported the syntheses of fj-polynitroporphyrins and the positively

shifted reduction potential of Zn(II), Ni(II)37,110 a n ( j M n ( I I ) l l l complexes of $-mSio-meso-

tetrakis(2,6-dichlorophenyl)porphyrins (15). The reaction scheme for the synthesis of 15 is shown

in Figure 1-11. Titration of Zn(TDCPP) (5b) with red fuming HNOJ-CFJSOJH-^SO^O

(1:0.12:0.06) selectively produces Z n ^ D C P P ^ O ^ J (15b) according to the amount of nitrating

agent used. The yields are 78, 90, 86, 93, 80, 95, 90, and 50 % for 15b with x = 1,2,3,4,5,6,7, and

8 respectively. 37
The Zn(II) complexes, 15b (x = 1 - 8) can be demetallated with acid to obtain

free-base 15a, which is subsequendy reacted with manganese(Ii) acetate to obtain M n

complexes. M n complexes bearing one to four P-nitro groups can be converted to

MnfTDCPPfNO^Cl (15£ x = 1 - 3) by treatment with gaseous HC1 in aerobic CH C1 . For 2 2

x = 5, the treatment with HC1 leads to a mixture of M n f T O C P P f N O ^ C l (15f: x = 5) and

M n ( T D C P P ( N 0 ) ) (15g: x = 5). For x = 6, 7, and 8, it is only possible

2 x to isolate the

M n t T D C P P t N C g j (15g: x = 6 - 8 ) . 47

(b) O x i d a t i o n studies

The electron-withdrawing effects observed as a result of nitration are remarkable.

Compound 15b (x=8, +0.155 V vs. S C E ) gives the highest reported first reduction potential of

1.44 V , positively shifted from 5b (-1.28 V vs. S C E ) . H 0 Manganese complexes of compounds

15f and g exhibit a remarkably wide span of Mn(IIi)/Mn(II) redox potentials that range from —

0.29 to +1.15 V (vs. S C E in CFLCkJ .47,111

 26

Ar=

v(N0 )x 2

N N

Ar
H +

Zn(TDCPP(N0 ) )
Zn(TDCPP) 2 x

5b X = 1 -8
15b

(N0 ) 2 x

For x = 1 - 4: Mn(TDCPP(N0 ) )CI2 x

15f(x = 1 -4)

i) Mn(OAc) 2
For x = 5 : Mn(TDCPP(N0 ) )CI
ii) HCI gas
2 x

and Mn(TDCPP(N0 ) )
in CH CI
2 2
2 x

1 5 f o r l 5 g (x = 5)
Ar
H TDCPP(N0 )
For x = 6 - 8: Mn(TDCPP(N0 ) )
2 2 x
2 x

X = 1 -8
15g (x = 6 - 8)
15a

Figure 1-11. Synthesis of P-polynitto-/»wo-tetakis(2,6-dichlorophenyl)porphyrins.

 27

Bartoli et al. studied the hydroxylation of anisole and naphthalene using manganese

complexes of 15 and H 0 2 2 as an oxygen transfer reagent and found interesting relationships

between the catalytic activity and the electron-deficiency of the metalloporphyrins.^ 7

Comparison of M n f T D C P P t N O ^ C l (15f: x = 1 - 4), M n f T D C P P ^ O , ) ^ (15g: x = 5 - 8) and

Mn(TDCPP)Cl (5f) (Figure 1-11) as catalysts showed that 15f (x = 1), 15f (x = 2), 15f (x = 3), and

15f (x = 4) gave 97, 96, 98, and 79 % yield respectively for the hydroxylation of anisole and 79,

83, 69, and 49 % yield respectively for the hydroxylation of naphthalene.^" 7

Regioselectivity

decreased as the number of nitro groups increased; for the hydroxylation of anisole, the product

ratio of (/wra-hydroxylated anisole/o^o-hydroxylated anisole) was 13, 11, and 9 and for the

naphthalene, (a-hydroxylated naphthalene/(5-hydroxylated naphthalene) was 10, 9, and 8 with

the catalysts 15f (x = 1), 15f (x = 2), and 15f (x = 3) respectively. Both the yield and the

regioselectivity for the hydroxylation of anisole by 15f (x = 1) were improved compared to the

results obtained with 5f.

Interestingly, the total yield of product obtained from the hydroxylation of anisole was

observed to be low when catalysts containing more than five nitro groups on the p-pyrrolic

positions were used, despite the increased electron-deficiency of the macrocycle. As an extreme

example, 15g (x=8) gave the oxidation products in less than 2 % yield for both anisole and

naphthalene hydroxylation.^ 7

(c) C o n c l u s i o n

P-Nitrated Mn(IIi)-porphyrins show increased catalytic activity compared to the second

generation catalyst, Mn(TDCPP)Cl (5f) (Figure 1-8). However, the number of P-nitro

substituents must be carefully controlled since over-nitration (more than five nitro substituents)
 28

results in a severe loss of catalytic activity. This may be due to the stability and catalytic inactivity

of the Mn(II) oxidation state under the influence of highly electron-deficient porphyrins.

(3) meso-Tetrakis(perfluoroalkjl)porphyrins

(a) Synthesis and o x i d a t i o n studies

There are three methods to synthesize »wo-tettaltis(perfluoroalkyl)porphyrins

(Figure 1-12). Two methods involve the synthesis of perfluoro-l-(2-pyrroryl)-l-alcohol (18),

which can be synthesized from the reaction of pyrrole and perfluoroalkyl aldehyde hydrate

(Path A) or the reaction of pyrrole and perfluoroacyl chloride (Path B). Pyrrole 18 undergoes

addition and cyclization in dry benzene to form porphyrinogen 19 that is oxidized to the

porphyrin 16a with D D Q . The yield obtained by DiMagno et al. for 16a (n = 3)

(OTWo-tetrakis(heptafluoropropyl)porphyrin) was 37 % based on 1 8 . 3 8

The yields obtained by

Golltf/'tf/. by this method for 16a (n = 1) (^j-o-tettalds(tjifluorometFiyl)porphyrin), 16a (n = 3),

and 16a (n = 7) (wwo-tetj:alds(pentedecafluoroheptyl)porphyrin) were 16, 38, and 34 % based on

18 respectively. ^ Alternately Wijesekera reported the synthesis of 16 via dipyrromethane 20 in

3

which the yields for 16a (n = 1) and 16a (n = 3) were 6 and 9 % respectively based on 20.112

The strong electron-withdrawing effect due to the perfluoroalkyl groups is reflected in the first

oxidation and reduction potentials of the Z n porphyrin. For example Z n porphyrin 16b (n = 3)

has +1.46 V (the first oxidation) and -0.72 V (the first reduction) vs. S C E , which are greatly

changed from +0.79 V and -1.39 V vs. S C E for Zn(TPP) (2b) (Figure 1-8) in P h C N . 3 8

There are only a few studies regarding Fe(II) and Fe(III) complexes of I6H 3
and catalytic

oxidation using these Fe complexes.48 According to Moore et al., the catalytic activity of Fe(II)

complex of 16 (16e) is the same as the second and the third generation catalysts
 29

H 0
> H
+ 2 O
Path A Path B
°Y C I
. O
N C F2n+1 N
Cn^2n+1 n

H
H

1 THF/triethylamine
2.NaBH 4

C H /molecular sieves, 4A
6 6

-4H Q 2

K . CnF2n+1
n r

C F n 1
n 2 + F 2 n + 1 C " n
/ C F +i
n 2 n

F
2n+lC ff
n
H
>
DDQ

Metallation

16b: M = Zn(ll)
16e: M = Fe(ll)

O N
H
THF/HCI

H H HO^OH o r H0^J0CH 3

20 Path C
C F2n+1 n Cn^n+I

Fi
g ur
e 1-12. Synthesis of wwo-tetrakis(perfluoroalkyl)porphyrins.
 30

Fe(TPFPP) (4e) and Fe(TPFPPBr ) (8e)

8 (Figure 1-8) in hydroxylation of isobutane and there was

a slight improvement of robustness of 16e from that of 4e and 8e.48 In order to conclude

whether Fe(II or III) (or other metal such as Cr or Mn) complexes of

wwo-tetraltis(perfluoroalkyl)porphyrins are effective as P-450 model compounds, more detailed

studies will be required.

3. Design conceptfor a new P-450 mimic

a. Basic concept

The basic concept for a new P-450 mimic was constructed based on the previous studies

of P-450 rnimics using electron-deficient porphyrins. It has been shown that electron-

withdrawing substituents are mandatory to protect the porphyrin macrocycle from oxidative

degradation and to enhance the reactivity of the oxo iron intermediate. However, as seen in the

oxidation studies using p-perfluoro-wwo-tetraarylporphyrins (

12-
14) (Figure 1-8) and P-polynitro-

^j o-tetralds(2,6-dicUorophenyl)porphyrins (15)
-
(Figure 1-11), extremely strong or plentiful

electron-withdrawing groups may deactivate the catalysts and/or facilitate decomposition of the

macrocycle by nucleophilic attack. Therefore, a moderate electronic effect would be ideal. Steric

effects should also be considered as an important factor, in order to increase the robustness of

the catalysts. Introduction of bulky substituents onto the porphyrin macrocycle prevents

unnecessary contact of the porphyrin core with oxidants (oxo metal intermediate, PhIO, R O O H ,

etc) and prevents the formation ofthe p-oxodimer which is catalytically inactive. 104,105

As a bulky and electron-withdrawing substituent, the trifluoromethyl group (-CF ) is a 3

good choice. Perfluoroalkyl groups have already been introduced on the OTW0-position 8,39 3
anc j

indeed on the P-pyrrolic positionsll4-U8 Q f porphyrins. However, there have been no literature
 31

reports o f the introduction o f trifluoromethyl (or perfluoroalkyl) groups o n the (3-pyrrolic

positions o f wwo-tetraarylporphyrins as far as the author is aware. A s ^wo-tetraarylporphyrins

have been well studied as P-450 mimics, the synthesis and characterization o f P~trifluoromethyl

(or perfluoroalkyl)-/W£f0-tettaarylporphyrins may provide potentially new and i m p r o v e d catalysts.

b. Potential advantages of trifluoromethyl substituents

A c c o r d i n g to the H a m m e t t equation,! 19 electton-withdrawing or electron-releasing ability

o f substituents can be expressed as a quantitative measure called substituent constant value (a).

Some substituent constant values are summarized i n Table 1-3. H i g h and positive o~ values

correlate to strong electron-withdrawing ability o f substituents.

Table 1-3. a values for different substituents.a

Substituent
-CF 3
0.54 0.43
-CH 3 -0.17 -0.07
-H 0.00 0.00
-F 0.06 0.34
-CI 0.23 0.37
-Br 0.23 0.39
-CN 0.66 0.56
-NQ 2 0.78 0.71
a
Values are from ref. 120,121. A s a typical reaction to
determine this quantity, ionization constants of the
carboxylic group i n substituted benzoic acids i n water at
25 °C has been s e l e c t e d ^ ; rj = l o g ( K / i Q , where K is the
ionization constant o f benzoic acid and is that o f
substituted benzoic acid, m and p denote that the O" value
was determined at meta and para substitution respectively.

A s s h o w n i n Table 1-3, the - C F group does not have the highest a values and thus it is
3

not the strongest electton-wididrawing group. H o w e v e r , due to the high electronegativity o f

fluorine (3.98 o n Pauling's scale)122 a n d relatively similar sizes o f the fluorine and hydrogen
 32

atoms (the van der Waal's radii of F and H are 1.35 and 1.20 A, respectively) 123 fluorinated

molecules have some unique properties. 124 The above-mentioned characteristics of fluorine

substituents increase the oxidative, hydrolytic, and thermal stability of fluorinated

molecules compared to the parent hydrocarbon (the C - F bond energy is about 116 kcal/mol.124

cf. the C - H bond energy of 104 kcal/mol.125). I n addition, the estimated van der Waals radius of

the trifluoromethyl group is at least 2.2 A126. Despite the similar sizes of - F and - H , the

trifluoromethyl group is slightly larger than the methyl group (2.0 A1

23)
. Thus, the thermal

stability and steric bulkiness of the trifluoromethyl group should be advantageous of the

protection of the macrocycle.

In summary, the unique electronic, steric, and physical properties of the —CF group may 3

be able to make P-trifluoromethyl-^j-o-tettaphenylporphyrin metal complexes ideal candidates as

potential P-450 mimics.

C. Sy
n t
h e
tc
i s
tr
ate
g y for P-
t
ri
fl
u or
o met
h yl
a t
i
o n of we
so-
t
e t
r
a phe
n y
p
lor
p hy
rn
i

Although 3,4-bis(trifluoromethyl)pyrrole is available in excellent yieldsl27,128 ; n o

condensation of this pyrrole with aldehydes to give a P-octalds(tofluorometliyl)-porphyrin has

yet been reported. Presumably, cyclization with aldehydes is unlikely due to the low electron

density at the a positions of the pyrrole. 129 Therefore, direct P-trifluoromeurylation of a

porphyrin is the preferred route to p-ttifluorometiiylporphyrins.

/. Brief overview of trifluoromethylation

The synthesis of perfluoroalkyl-substituted aromatics falls into three classes.

 33

a. Fluorination of an existing aryl substituent (Scheme 1-3)

As examples of this category, (a) substitution of chloride substituents of a trichloromethyl

group with antimony trifluoride or hydrogen fluoride^O and (b) fluorination of a carboxylic acid

by sulfur tetrafluoride with hydrogen fluoride as a catalyst^ ! have been reported. Obviously, the
3

drawbacks of the use of these methods include challenges in the preparation of appropriately

substituted ^j-o-tetraphenylporphyrins and technical difficulties associated with the handling of

SbF , H F and SF .132 Therefore, the application of these methods is limited.

3 4

00 rr Ch3
°' » fY° *
2 a
SbF orH
3 F > > ^ r - C F
3

C 0 0 H
SF 4 H F (cat.)
(b)

Sc hem e 1-3. Fluorination of an existing aryl substituent. (a) Substitution of

chloride substituents with fluoride, and (b) fluorination of a carboxylic acid.

b. Introduction of trifluoromethyl groups

(1) Transfer of CF f (Scheme l-4(a))

Perfluoroalkyl organometallic reagents have been studied extensively and it is known that a

number of them, especially those of copper, mercury, cadmium, and zinc, are useful reagents for

trifluoromethyl anion transfer to organic compounds. 1 3 3

Some organosilicon perfluoroalkyl

compounds are also good trifluoromethyl anion transfer reagents, although only a few

applications to aromatic compounds have been reported. ^ ^ 3

 34

X CF,
(a)
e.g. CF3M or
(CF ) M
X=Ior Br
3 2

M=Cu, Hg,
Cd, or Zn

(b)
02N O^Ci N02 ^
F C 3

22 ,
dryTHF

Sch em
"4
e 1-4. Introduction o f a trifluoromethyl group.(a) Transfer o f CF ~, 3

and (b) transfer o f C F . 3

+

(2) Transfer of CF }
+
(Scheme 1-4(b))

Electrophilic perfluoroalkylating reagents are also k n o w n . Indeed, T a m i a k i ^ / a / .

synthesized (3- and ^j o-tafluoromethyl-5,15-bis(3,5-di-Abutylphenyl)porphyrins (21)

-
using S-

(tofluoromethyl)-3,7-dinitrobenzothiophene trifluoromethanesulfonate (22) i n dry THF.^8

H o w e v e r , the yields were p o o r w i t h a mixture o f regioisomers obtained (16% o f 23, 4 % o f 24,

and 1 % o f 25 for M = Z n ( I I ) ) and 55 - 62 % o f starting materials were tecovered. U n l i k e p-

halogenation34,44,70-77 o r n i t r a t i o n , this m e t h o d seems to be inefficient for the modification

37

o f p-pyrrolic positions.
 35

O f the above-mentioned methods and reagents, perfluoroalkylcopper reagents have

received more attention than any other perfluoroalkyl organometallic compounds due to their

ease of preparation and ready availability. 133 A number of examples of perfluoroalkylation of

aromatic compounds have been reported. 133 However, there are no literature reports of the

application of perfluoroalkylcopper reagents to porphyrins.

2. Copper assisted trifluoromethylation

The pioneering work of McLoughlin and Throwerl32 a n c J Kobayashi ^i?/. 136,137

identified trifluoromethyl copper reagents as ideal coupling reagents for trifluoromethylation of

aromatic halides. Perfluoroalkylcopper reagents have been prepared by the following three

methods: (i) reaction of C F I or C F B r with metallic copper in a coordinating solvent at elevated

3 2 2

temperatures 132; (ii) pyrolysis of tafluoroacetate in the presence of Cu(T) halides!36,137.

(iii) metathesis reactions of mfluoromethylorganometallic reagents with metallic copper or Cu(T)

halides. In method (i), there is a technical difficulty in handling the precursors (in spite of the

high temperature (100-140°C) of the reactions, the b.p. of perfluoromethyl halide is low, e.g.

CF I: —22.5°C) and another major drawback is the high cost of the perfluoroalkylhalide.133
3

Methods (ii) and (iii) do not require special equipment and the cost of the materials are

reasonable. 133 Methods (ii) and (iii) are detailed below.

a. CF Cu from pyrolysis of sodium trifluoromethyl acetate in the presence of Cu(I) halide

3

Trifluoromethylation via pyrolysis of sodium or potassium trifluoromethylacetate in the

presence of Cu(I) halide is the least costly and least hazardous methodology for introduction of

the trifluoromethyl group into aromatic compounds.133 As shown in scheme 1-5 (Path A), in

the presence of Cu(I) halide, pyrolysis, or decomposition (decarboxylation) of sodium

 36

NMP
Arl + C F C 0 N a / C u l
3 2 • ArCF 3 (Path A)
1 4
° - 1 6 0
° C
40-78o/ 0

-^U- CF H 3 + ArH (Path B)

(side products)

Scheme 1-5. Trifluoromethylation of aromatic halide by pyrolysis of C F C 0 N a . 3 2

trifluoroacetate in aprotic polar solvents such as N-methylpyrrolidone (NMP) or D M F at around

150 °C generates the active trifluoromethylating agent C F C u and copper assisted substitution
3

gives the trifluoromethyl aromatic compound. Residual water, which largely arises from the

hygroscopic trifluoroacetate salt, causes serious problems including loss of active C F C u and 3

dehalogenation of the substrate to form fluoroform and hydrogenated aromatic compounds as

shown in Path B. In order to minimize the side reaction, Freskos^8 employed a toluene-

azeotrope to distill off any trace water before the reaction temperature was brought up to

155 °C (Figure 1-13). With this method, only two equivalents of perfluorocarboxylate are

required and the yields of the products were moderate to excellent.

toluene + water CF CF2 3

distillation at 155 °C
120°C 2h
toluene 90 %
DMF
CF CF C0 K
3 2 2

Cu?
trace water

Fi
g ur
e 1-13. Removal of water by use of a toluene-azeotrope in the
pentafluoroethylation of a-iodonaphthalene.
 37

b. CF Cu from metathesis of trifluoromethylcadmium with Cu(I) halide

}

(1) Trifluoromethylation

B u r t o n et al. showed that difluoromemylcadmiurn, C F - C d (a mixture o f C F C d X and

3 3

( C F ) C d , X = C 1 or Br) is an excellent precursor for generation o f the active C F " transfer agent,
3 2 3

CF Cu,
3 and can b e used for high-yield multiple trifluoromethylation o f aromatic

halides. 133,139,140 -phg tnfluoromemylcadmium reagent undergoes metathesis, or an exchange

reaction w i t h Cu(I) halide to give C F C u at - 40°C i n 90 - 100 % yield ( 1 . 2 ) .

3
1 4 0
In-situ generated

(CF)Cd32 Cu
X ^ C F 3 C u

UhU
3dBr -40°C

C F C u then attacks the brominated or iodinated site o f aromatic compounds. 133,139

3 s ^ e

reaction is perfluoroalkyl chain oligomerization w h i c h occurs at higher temperature (equations

(1.3) a n d (1.4)).133 However, addition of the same volume of

hexamethylphosphoramide ( H M P A ) to the volume o f trifluoromethylcadmium reagent, w h i c h is

given at 1 M i n D M F solution,139 inhibits the oligomerization.133

CFCu 3 y »» CCFCu
F
3 2 (1.3)

DMF
CFCu 3 • CF(CF)Cu 3 2n (1.4)
90-100°C

(2) Synthesis of trifluoromethylcadmium

Trifluorometiiylcadmium is synthesized from dibromodifluoromethane and c a d m i u m

powder i n D M F . T h e proposed reaction mechanisms!39 r e s h o w n i n equation (1.5) - (1.11).

a

T h e reaction is initiated by electron transfer from c a d m i u m to the electronegative carbon i n

C F B r (1.5). T h i s is followed by a second electron transfer to facilitate the loss o f bromide

2 2

ions (1.6) and to give a reactive difluorocarbene (26) (1.7). T h i s species reacts w i t h D M F (1.8)
 38

and the resultant dimemyl(iifluoromemylamine (27) releases fluoride ion (1.9) which reacts with

another molecule of difluorocarbene to form a trifluoromethyl anion (1.10). Finally the C F ~ ion 3

combines with CdJ3r or C d+ 2 +

to form C F C d B r and(CF ) Cd, respectively (1.11).
3 3 2

CF Br 2 2 + Cd Cd [CF Br ]*
+
2 2 (1.5)

Cd [CF Br f
+
2 2 - Cd 2 +
+ [ C F B r ] " + Br" 2 (1.6)

[CF Br]" 2 • : C F + Br" 2 (1.7)

:CF 2 + (CH ) NCH=0 3 2 *~ ( C H ) N C F H + C O

3 2 2 (1.8)
26 27

(CH ) NCF H
3 2 2 ^ [ ( C H ) N = C F H ] + F"
3 2
+
(1.9)
27

:CF 2 + F" - CF " 3 (1.10)

26

CF " 3 Br and C d 2
^ ( C p ) 3 2 C d + C F CdBr
3 (l.il)

Thus, Cu(I) assisted trifluoromethylation is an efficient method for the preparation of

trifluoromethylated aromatic compounds.

D. Anal
y si
s of por
p hy
rn
is

/. UV-visible absorption spectroscopy

a. Characteristics of UV-visible absorption spectra ofporphyrins and metalloporphyrins

Porphyrins exhibit characteristic absorption properties in the UV-visible region. 141,142 j n

Figure 1-14, UV-visible absorption spectra of free-base, diprotonated, and metallated (with
Fi
g ur
e 1-14. U V - v i s i b l e spectra o f /^.ro-tettaphenylporphyrins i n C H C 1 . 2 2

(a) H T P P (2a)
2 (solid line) and H T P P
4
2 +
(narrow line), (b) Z n T P P (2b). "
Q bands are multiplied b y five.
 40

Zn(II)) forms o f ^.ro-teteaphenylporphyrin (TPP) are shown. Porphyrins show an intense

absorption near 400 n m (s ~ 4 x 1 0 M ' c m ) , w h i c h is referred to as the Soret band (also called
5 1

the B band). Porphyrins also exhibit less intense bands, usually found between 500 and

700 n m , w h i c h are referred to as the Q bands.141,142 - p h origins o f the Soret and the Q bands
e

are 71-71* excitation from the ground state to the second and the first excited singlet state,

respectively. 142 T h e Q bands split into two bands!42 for porphyrins such as Z n ( T P P ) (2b)

(Figure 1-8) as shown i n Figure l-14(b). T h e lower-energy band o f the t w o Q bands, w h i c h is

referred to as Q (0,0), corresponds to the excitation o f an electron from the ground to the

lowest-energy excited singlet state and the higher-energy band, Q (1,0), including one mode o f

vibrational excitation. 142 F o r the free-base, each Q band is further split into two bands due to

the breaking o f the D 4i symmetry o f the porphyrin ring by the central p r o t o n axis as D 2/l

symmetry is achieved (Figure 1-15).142 T h u s , Q (0,0) and Q (1,0) split into 0,(0,0), Q (0,0) and y

Q (1,0), Q (1,0).142
X T h e addition o f acid to the free-base results i n protonation o f each inner

nitrogen and the spectrum of porphyrin dication (Figure 1-15) returns to the

D - t y p e (Figure 1-14(a) (gray line). 142

4h

2+

2+
H TPP
2 [H TPP]
4

D 4h

Figure 1-15. Symmetries o f Z n ( T P P ) (2b), H T P P (2a) a n d [ H T P P ]

2 4
2
 41

b. Electron-withdrawing effects on UV-visible absorption spectra

Electron-withclrawing substituents stabilize the highest occupied molecular orbital

( H O M O ) (ft) and the lowest unoccupied molecular orbital (LUMO)(7t*) orbitals of

porphyrins.143 Since UV-visible spectra of porphyrins reflect the 7t-7t* electronic transition,

changes in the UV-visible absorption spectra are observed if the H O M O and the L U M O are

affected (differently by the electronic effects of substituents.39,144 j n o n e c a s e ; such as in the

example shown in Figure 1-16, (only Q bands are shown - the Soret band also shifts to a longer

wavelength)!41 it is known that replacement of an ethyl group of etioporphyrin I (28)

; with a

electton-withdrawing carboxylic group results in a red-shift of the UV-visible bands in

rhodoporphyrin X V (29). The red-shifts of the absorption bands imply contraction of the

HOMO-LUMO gap. Alternatively, replacement of ^jo-phenyl groups of H TPP

2 (2a)

(Figure 1-8) with pentafluorophenyl groups to give H T P F P P (4a)2 (Figure 1-8) causes the bands

to shift from 418 (Soret), 514, 549, 590, and 646 nm (Q bands) for 2a in C H C 1 to 410, 505, 2 2

535, 582, and 645 nm for 4a, i.e. a minor blue-shift. This phenomenon implies that the H O M O -

L U M O gap is expanded by the electton-withdrawing effect of the wwo-perfluorophenyl groups.

The blue-shifts of the absorption bands are also observed in P-perfluoro-wwo-arylporphyrins,

12a, 13a, and 14a (Figure 1-8) from H TPP.

2 Accordingly, either HOMO-LUMO gap

contraction (red-shift) or expansion (blue-shift) may occur due to the introduction of electton-

withdrawing substituents. Unfortunately, it is rare to observe a pure electronic effect of

substituents on the UV-visible spectra, for it is well known that macrocycle distortion causes red-

shifts in UV-visible absorption bands of the porphyrin.144-147 p o r example, the UV-visible

spectrum of severely distorted Zn(II) complex of P-octamethyl-«?wo-

tettaphenylporphyrin (Zn(OMTPP)) (30) (p.43)(442, 574, and 630 nm in C H . C L ) 1 4 7

shows
 500 550 600 650 500 550 600 650

Wavelength (nm) Wavelength (nm)

Porphyrin 2 3 7 8 12 13 17 18
Etioporphyrin-I (28) Me Et Me Et Me Et Me Et
R h o d o p o r p h y r i n - X V (29) Me Et Me Et Me C0 H P H Me
2

5, 10, 15 and 20 = H , M e = m e t h y l , E t = e t h y l , P H
= CH CH C0 H
2 2 2

Fi
g ur
e 1-16. E x a m p l e o f the U V - v i s i b l e spectral change by electton-withdrawing
effects. U V - v i s i b l e spectra were adapted f r o m reference 141.
 43

enormous red-shifts compared to Z n ( T P P ) (419, 548, and 582 n m i n C H j C L ) . Macrocycle

distortion causes destabilization o f the H O M O w h i c h also leads to contraction o f the H O M O -

L U M O gap, and thus the red-shifts o f the absorption b a n d s . 1 4 4

" 1 4 6

Z n ( O M T P P ) (30)

2. Redox potentials ofporphyrins

a. General redox properties of porphyrins in non-aqueous media

(1) Technique, solvent, and supporting electrolytes

A l t h o u g h redox properties o f porphyrins have been studied by various techniques 1 4 8

,

cyclic voltammetry has been the m e t h o d o f choice for the investigation o f the electrochemisty o f

porphyrins, 1 4 8
' 1 4 9
and several solvents such as D M F , D M S O , M e C N , B u C N , P h C N , or

C H C 1 have been used. 9 , i 5 0 Q

2 2
1 4
n e Q f fa most c o m m o n solvents is C H C 1 due to its weak
e 2 2

binding properties, ability to solubilize porphyrins and its large cathodic and anodic range close

to ± 1.9 V vs. S C E . 5 0 Therefore, a wide range o f redox potentials can be studied i n C H C 1 . 5 0

1
2 2
1

T h e most c o m m o n supporting electrolytes, w h i c h are used to increase the conductivity o f the

solution, are tetrabutylammonium perchlorate (TBAP), tettaethylammonium perchlorate

(TEAP), tetrabutylammonium tetrafluoroborate (TBABF ), 4 and tetrabutylammonium

hexafluorophosphate ( T B A P F J i n w h i c h C 1 0 , B F " , and P F " can be considered as n o n - b i n d i n g

4 4 6

anions. A l l o f the salts are highly soluble i n non-aqueous solvents.

 44

(2) Porphyrinringredox properties in free-base and metalloporphyrins

Ftee-base and many metalloporphyrins undergo two one-electron oxidations and two one-

electron reductions, all of which occur at the conjugated 7t-ring system of the porphyrin

macrocycle. 1^0 Figure 1-17 shows the cyclic voltammogram of H T P P (2a)

2 in CH C1 , which
2 2

reveals a typical example of two one-electron oxidations and two one-electron reductions. The

former reactions correspond to the movement of two electrons from the H O M O and to the

L U M O . Therefore, the difference in the half-wave potentials for the first oxidation and the first

reduction, E ° ( l ) - E, / (1), is considered to correspond to the size of the H O M O - L U M O

/2
r
2

gap. 1 4 9
- 1 5 0
A systematic study showed that E™ (1) - E $ ( l ) = 2.25 ± 0.15 V and constant
2

differences between E,%(1) and E° (2)) (=AE ° ) and between E $ ( l ) and E$(2) (=AE / ) were
/2 1 /
X
2 1
re
2

observed for 25 metal complexes of octaethylporphyrin (OEP).151 The H O M O - L U M O gap,

E ° ( l ) - E{/ (1) = 2.25 V approximately agrees with the theoretically calculated value of 2.18 eV
/2 2

for most metalloporphyrins.152 A similar experimental observation was also obtained for the

different metal complexes of TPP.153 Thus, ring redox potentials of a porphyrin are pretty

much constant throughout the free-base and the series of metal complexes.

(3) Iron porphyrins

As this thesis describes some electrochemistry of iron porphyrins, redox properties of iron

porphyrins are briefly described here.

Most synthetic iron porphyrins show three to four electron transfer reactions in a variety

of nonaqueous solvents. 150 Figure 1-18 shows a cyclic voltammogram of Fe(TPP)Cl (2d)

(Figure 1-8) measured by the author. A reduction Fe(III) to Fe(ir) generally occurs between +0.2

and —0.5 V vs. SCE.150 The most negative reduction potential shown could be Fe(II)/Fe(T) or
 Ph

2a

E (2): p —> p-+

] / 2
2 +
+ e <—

E l 7 (l):
2 p-+ + e" <- P

P + e" -> P'-

<—

Ev (l): 2 P'- + e" <- -> p2-

l i i i i

M
E°; (2)
2

rf
i
1 - r - i ^ /r\\
re

1E 1 / 2 (2)
r 1
H O M O - L U M O gap j
1 , j
E^O) Er; (i)
2

i i i i •
•1.50 M . 0 0 »0.50 0.00 -0.50 -1.00 -1.50

V vs. S C E

Figure 1-17. Cyclic v o l t a m m o g r a m o f H T P P (2a) i n C H C 1 , 0.1 M T B A P ;

2 2 2

scan rate, 50 m V / s . A d a p t e d f r o m reference 149.

Fi
g ur
e 1-18. Cyclic voltammogram o f F e ( T P P ) C l (2d) i n C H C 1 , 0.1 M T B A P F
2 2 6

scan rate, 100 m V / s ; F c / F c +

= ferrocene/ferrocenium coupling, 0.46 V vs. S C E .
 47

Fe(II)/(Fe(II) porphyrin 7t-anion) couple.150 -ph assignment of this potential has long been a
e

subject of controversy. 154,155 Some studies show the likeliness of the assignment of Fe(I)

depending on the solution conditions and porphyrins.150 Each anodic reaction around ~1.1 V

and ~1.6 V corresponds to removal of an electron from the T P P macrocycle. 150

b. Effects of substituents on the redox potentials of derivatives of TPP

(1) Aryl-ring-substituted TPPs

Kadish and Morrison measured half-wave potentials of seven H TP(/)-X)P (31a) ((/>-X) 2

represents the para positions of meso-phenyl groups are substituted by substituent X) in various

solvents. 156 In order to analyze the results quantitatively as a function ofthe substituent, Kadish

and Morrison employed the Hammett linear free energy equation and expressed a relationship as

shown in equation (1.12), where E * 2 and E , " 2 are the half-wave potentials for T P P substituted

AE 1 / 2 = E* 2 - E ^ = erp (1.12)

with X and H at the phenyl para-position, respectively, andCTis a Hammett constant for X , and

p is a constant value under the same experimental conditions. As shown in Figure 1-19, plots of

E 1 / 2 values vs. 4CT for each electrode reaction were linear, indicating that macrocycle oxidations

become more difficult and reductions become easier as the substituents become more electron-

withdrawing. 156

Similarly, five electrode reactions (P-Fe(T)/P~"-Fe(I), where P is porphyrin, in addition to

the four electrode reactions in Figure 1-18) were examined for nineteen different

FefTPf>X)P)Cl (31b) and Fe(TP(w-X)P)Cl (32b) systems. Linearity of the E 1 / 2 vs. 4CT for these

reactions in C H C 1 2 2 was observed. 157 Linearity of the plots was also observed for other
 49

metaUoporphyrin species such as those containing C o ^ I ) ^ Mn(III) 59,160 Cu(II) 0, and

1 1
>
16

Zn(II). 0
16

(2) B-Substituted TPPs

The electrochemistry of P-substituted TPPs has been analyzed in two ways. The first

method of analysis involves a series of p-mono-substituted TPPs with different substituents. The

second analysis involves the series of TPPs P-substituted with zero to eight substituents of the

same kind.

(a) P - M o n o - s u b s t i t u t e d T P P s with different substituents

Giraudeau et al. examined the ring redox potentials of T P P substituted at a p-pyrrolic

posistion by substituent X (H TPP(X)) (33) in C H C 1 .

2 2 2
1 6 1
As observed in the phenyl substituted

TPPs, (Figure 1-19), E 1 / 2 vs. 4a plots showed that the oxidation and the reduction potentials

increase almost linearly with the increase of a value of the substituents. 161

33

X = H , O E t , Br, CI, C N , N Q 2
 50

(b) P - S u b s t i t u t e d T P P s w i t h m o r e t h a n o n e s u b s t i t u e n t o f t h e s a m e kind

Giraudeau et al. studied a series o f P-cyano-wtf.ro-tettaphenylporphyrins (34). Figure 1-20

shows plots o f the first oxidation and reduction vs. the number o f substituents for the free-

base (34a) and the C u complex (34c).161 Analysis o f the plots i n Figure 1-20 (p.51) reveals that

the reduction potentials change linearly w i t h the number o f cyano groups but that plots o f the

oxidation potentials are non-linear for b o t h free-base and C u complexes.

Extreme cases o f the non-linearity o f the E 1 / 2 for the oxidation vs. number o f substituents

are shown by K a d i s h eta/., w h o measured the redox potentials o f a series o f P-brominated T P P

derivatives (35). 162-164 Figure 1-21 (p.52) shows the plots o f E 1 / 2 for the first oxidation and

reduction vs. extent o f brornination for 35a. 162 F o r the first reduction, (Fe(in)/Fe(II)) linearity

is maintained, but this is n o t the case for the oxidation; the first oxidation potential is m a x i m i z e d

at x = 2 for 35a as shown i n Figure 1-21.162 Similar results were obtained for Zn(II) complexes,

35b.l64

Ochsenbein et al. demonstrated, by using cyclic voltammetry and X - r a y crystal structure

studies, that conformational changes within molecules affect the redox potentials o f

P-halogenated tetraarylporphyrins (36 - 39).165 Crystal structures o f 3a and 36 - 38 (/mo-mesityl

groups omitted i n the diagrams o f the X - r a y crystal structures) show that the macrocycle is

progressively distorted as the size and number o f the substituents increases. This is presumably

due to increased steric interactions between the substituents (Figure 1-22 (p.53)). Table 1-4

(p.54) shows the first reduction and oxidation E 1 / 2 for 3a and 36 - 38. Regardless o f the nature

o f the substituents, the increase o f the E f c

2 ( A E ^ ) w i t h increasing number o f the substituents is
2
 -1.5"
0 1 2 3
# of C N group

Figure 1-20. First reduction(O) and oxidation potentials (•) vs. # of C N groups
for (a) H T P P ( C N ) (34a) and (b) C u T P P ( C N ) (34c). The plots were produced
2 X x

from the values reported in reference 161.

Figure 1-22. Side view of the crystal structures of H T M P (3a), H T M P C 1 (36)
2 2 4

H T M P B r (37), and H T M P C 1 (38) (the meso-mesityl groups are omitted for

2 4 2 8

clarity). Adapted from reference 165.

 54

almost constant (— +0.3 V), while A E 1 / 2 is obviously lower in the severely distorted porphyrins

than in the planar macrocycles. This infers that the H O M O is destabilized by macrocycle

distortion. The results shown in this section correlate to the red-shifts ( H O M O - L U M O gap

contraction) observed in the UV-visible spectra which also correspond with macrocycle

distortion (see section D.l.b.).

Tabl
e 1-4. The first reduction and oxidation potentials for 36 - 39. a

Halogen pRed
Porphyrin
substituents ^1/2
T7Rcd
^1/2 AE*1
3a — -1.41 +0.91
+0.29 +0.24
36 4C1 -1.12 +1.15
+0.27 -0.10
38 8C1 -0.85 +1.05

3a -1.41 +0.91
+0.32 +0.21
37 4Br -1.09 +1.12
+0.25 -0.13
39 8Br -0.84 +0.99
a
E in V vs. SCE: solvent CH C1 , electrolyte T B A P F . T=25 °C,
1 / 2 2 2 6

ref.165

(3) Conclusion

In summary, for porphyrin macrocycles without conformational change, the presence of

election-withdrawing effects linearly increases both the first reduction and the first oxidation

potentials. This is the case for phenyl-substituted and P-mono-substituted TPPs. However, when

the macrocycle is distorted, an expected increase in the first oxidation potential by an electron-

withdrawing effect is offset by destabilization of the H O M O due to macrocycle distortion, while

linearity for the first reduction potential (ring reduction or Fe(III)/Fe(II)) vs. an expected

electron-withdrawing effect is maintained. Therefore, one can deduce the electron-withdrawing

 55

effects imposed upon a porphyrin macrocycle by comparing the first reduction potential of one

porphyrin with the value of another.

3. H NMR
1
spectroscopy

a. Porphyrin ring current effect

' H N M R spectroscopy of porphyrins is a valuable technique to enable analysis and

characterization. Chemical shifts observed in ' H N M R spectra of diamagnetic porphyrins can be

assigned and rationalized by considering the porphyrin ring current effect which is characteristic

of aromatic c o m p o u n d s . ! ' ! 66 67
p o r a n aromatic system such as a porphyrin, the magnetic

deshielding resulting from the ring current is positive for nuclei on the outside of the ring current

(for meso and P-substituents), and negative for nuclei positioned within the ring current (for N - H

proton). i 6 6
jl 6 7
This shielding and deshielding results in massive chemical shifts of signals

compared to those of signals due to non-aromatic systems. Figure 1-23 (p.56) shows the ' H

N M R spectrum of H T P P (2a) 2 in CDC1 3 at 298 K recorded by the author. A remarkable

deshielding effect due to the induced paramagnetic field that is caused by the ring current is

observed as a downfield shift of the signal due to the p-pyrrolic proton (8.86 ppm) of the

porphyrin compared to that of pyrrole (~6 p p m ) . 1 6 7

> 1 6 8
O n the contrary, the N - H proton is

strongly shielded by the induced diamagnetic field and the effect is observed as an enormous

upfield chemical shift (-2.76 ppm) of the porphyrin N-H compared to that of

N - H signal (7-12 ppm) in pyrrole i t s e l f . 1 6 7

' 1 6 8

b. Concentration effect

It is well known that porphyrins aggregate in s o l u t i o n 1 6 6

' 1 6 9
and this phenomenon has

been extensively studied in solution using N M R spectroscopy. 0-172 j± typical experiment to 17

 a
2a

a: P-pyrrole H (8.86 ppm)

b: ortbo-phenyl H (8.22 ppm)
c: meta,para-phenyl H (7.76 ppm)
d: N - H (-2.76 ppm)

I ' 1 1 1
I ' ' 1
' I 1
' ' 1
I 1
' ' ' I ' ' 1 1
I 1 1
I 1 1 1 1
I ' ' '-r-p-"-i-p-'-'-H ' ' ' ' I ' ' ' 1
I 1
' ' '-T'-i-r-r
10 9 8 7 6 5 4 3 2 1 0 -1 -2 -3
Chemical shift (ppm)

Fi
g ur
e 1-23. 200 M H z H N M R spectrum of H T P P (2a) in C D C 1 at 298 K .
X
2 3
 57

detect aggregation of porphyrins is to measure the chemical shift at various

concentrations. 71,172
1
Figure 1-24 (p.58) shows the change of the chemical shift due to

meso-ptoton of 40a with the concentration change, according to Ono etal.^72 rj ue t o

71-71 aggregation, the chemical shift of the shielded meso-ptoton is shifted by the induced

diamagnetic field of the porphyrins. Furthermore, the same experiment with 40b showed that

less aggregation occurs compared to the electron-deficient 40a (the result for 40b is not

shown). The reason why the electron-deficient porphyrin tends to aggregate more is not well

understood.

c. N-H tautomerism

Figure 1-25 (p.59) shows the N - H tautomerism for ^jo-tetraphenylporphyrin. Several

other tautomers are also possible by locating two inner protons on adjacent nitrogens! 66
(the

structures are not shown) but they are less stable due to penetration of each hydrogen into the

van der Waals sphere of the other.! ! Although two tautomers (41a
4
and 41b) exist as the most

probable structures! ! for H T P P , H and H cannot be distinguished using N M R spectroscopy

4
2
A B

due to the fast exchange between 41a and 41b on the N M R time scale at room temperature.! 66

In other words, H T P P of symmetry D

2 2 h is observed as an average of 41a and 41b of D 4 h

symmetry at room temperature by N M R spectroscopy. However, this exchange is slowed below

220 K and two signals for H and H can be observed.! ,174 As shown in Figure 1-25, H is
A B 73 A

located on the conjugated 187t-electron pathway (presented by the dotted line) and H is located B

on the isolated double bonds.

Crossley et al. studied tautomerism of sixteen different (3-mono-substimted-TPPs (42) by

*H N M R spectroscopy at 200 K in C D C 1 and found that the position of the N H tautomeric

2 2
Fi
g ur
e 1-24. Plot of chemical shift of meso-H vs. porphyrin concentration
for 40a. Adapted from reference 172.
 59

Fi
g ur
e 1-25. Tautomerism in H T P P 2 (2a). Ellipses indicate isolated
double bonds.

equilibrium is affected by the nature of the s u b s t i t u e n t s . A s shown in Figure 1-26 (p.60), for

R = C N , N 0 , O C O P h , C l , Br, C H O , O M e , SPh, N H C O M e , and O H G g Y electron-

2
ar el

withdrawing groups) the dominant tautomer has the substituent positioned on an isolated double

bond. For R = C H = C H , N H , ( C H ^ M e , Me, and C H M e , the major tautomer has the

2 2 2

substituent positioned on the aromatic derealization pathway. Thus, the effects of electron-

withdrawing substituents may be appreciated by analysis of the ' H N M R spectra of porphyrins at

low temperature, and assessment of N H tautomerism observed therein.

4. Spectrophotometric titration

In this section, two techniques for the evaluation of electron-deficiency of a porphyrin by

spectrophotometry are described.

a. Evaluation ofpK o/NH a

2+ P 4
K
+ P3
K
PK 2 PKI o
PH 4
2
• PH, • PH • ? PH" — - P "
2
(
1 .
1 3)

The free-base parent porphyrin (PEQ can be protonated twice on its imine type nitrogen

atoms to form mono- (PH ) or di-cation (PH 3

+
4
2+
) species, or can lose two pyrrole type protons
 Ph Ph

42a 42b

42a R 42b
>99 CN -
97 N0 2 3
94 OCOPh 6
94 CI 6
91 Br 9
84 CHO 16
82 OMe 18
81 SPh 19
73 NHCOMe 27
61 OH 39
38 CH OH
2 62
33 CH=CH 2 67
22 NH 2 78
21 (CH^Me 79
19 Me 81
9 CHMe 2 91

Fi
g ur
e 1-26. Relative populations of 42a and 42b at 200 K in CD C1 .
2 2

Adapted from reference 175.

 61

to produce mono- (PH') or di-anion (P ~), equation (1.13). 2 169

The values p X and pi<C have been
3 4

well documented to be between 3 and 9.141,169 Q n m e con t r a r y , piC, and pK are estimated to
2

be in the order of 1 6 ^ 76
and have not been studied well.

Recently, Woller and DiMagno have determined the piC, values of P-octafluoro-w&ro-

tetraarylporphyrins H T P P F (12a)
2 8 and H T P F P P F (14a)
2 8 (Figure 1-8, p. 11) by

spectrophotometric titration with D B U in CH C1 .36 The titration showed a difference of +3.9

2 2

and + 0.2 xpK a units from D B U for 12a and 14a, respectively. Since this method of analysis is

performed in a common solvent for porphyrins (CH^Cy, it should be applicable to other

electron-deficient porphyrins in order to assess the extent of electron density withdrawal from

the macrocycle by the substituents.

b. Determination of central metal — ligand binding constant

PCo(ll) + B - PCo(ll)B (1.14)

K2

PCo(ll)B + B • PCo(ll)B 2 (1.15)

P = porphyrin, B = Lewis base

It is known that Lewis bases such as pyridine bind to four-coordinate porphyrin cobalt

complexes as shown in equations (1.14) and (1.15). 177-180 Walker studied the axial

coordination of Co(TP(p-OCH )P) (43) 3 (p.62) with amines to investigate the electronic and steric

influence on the 0 2 binding behavior of the Co(II) porphyrin complex.178 Lrn et alX^^ and

Smirnov ^(2/180 evaluated the electron-deficiency of the Co(II) complex of

P-cyanoporphyrin (34c) and Co(II) complexes of P-octafluoroporphyrins (12h and 14h),

 62

Ar'
43

respectively. As summarized in Table 1-5, electron-deficient porphyrins show higher log lvalues

than that of 43, that is, 34c, 12h, and 14h bind pyridine more tighdy than 43.

Thus, central metal-axial ligand binding constants may also be determined by

spectrophotometric titration and the electron-deficiency of porphyrins can be evaluated by

comparing the binding constants.

T ab l
e 1-5. Formation constants for pyridine
binding in C H C 1 at 25°C
2 2

Porphyrin log*; logK 2 Reference

43 2.7 178
34c 4.2 -0.35 179
12h 4.3 -0.08 180
14h 5.9 1.03 180
 63

Electron-deficiency alone may not guarantee high efficiency and robustness of porphyrin

catalysts but now we are sure that electron-deficiency is a necessity for the desired oxidation

catalyst. Thus, evaluation of the electron-deficiency of porphyrins is important in the

development of P-450 mimics. As shown above, UV-visible, 1

H NMR spectroscopy,

electrochemistry, X-ray crystallography, and spectrophotometic titration can all be used, alone

and in combination, to assess the effects of electron-withdrawing substituents on the properties

of porphyrins and metalloporphyrins.

E. Goa
s
l of t
h i
sthesi
s

The overall goal of this thesis is to contribute to the research field of cyctochrome P-450

rnirnics. The initial approach in search of an active and robust metalloporphyrin as a P-450

mimic was to prepare novel electron-deficient (3-trifluoromethyl-^j'o-tetraphenylporphyrins

including Zn(II), Co(II), and Fe(III) complexes of the species. The major part of this thesis

concentrates on analysis of the electron-deficiency of the porphyrins by the UV-visible and

N M R spectroscopies, cyclic voltammetry, and X-ray crystallography. In order to make the

properties of the novel porphyrins clearer, the results of analysis are compared with known

electron-deficient porphyrins. Electron-releasing P-methyl-wtfJo-tetraphenylporphyrins were also

prepared to show an interesting comparison with P-trifluoromethylporphyrin in electronic and

structural effects of the substituents. Finally results of oxidation of cyclohexane and cyclohexene

using Fe(III) porphyrins as catalysts are shown, and the usefulness of P-trifluoromethyl-OTwo-

tetraphenylporphyrins as P-450 mimics is discussed.

 64

CHAPT
E R II

Resul
t
s and Di
s cussi
o n

A. Sy
n t
h e
ss
i of P-
t
ri
fl
u or
o met
h yl
- and p-
m e
thy
-
lme
so-
t
e t
r
a phe
n y
p
lor
p hy
rn
is

The trifluoromethyl group may be an advantageous substituent when directly introduced

onto the porphyrin macrocycle in order to improve the efficacy of metalloporphyrins as catalysts

for oxidations due to its strong electron-withdrawing effect, bulkiness and stability (Chapter I,

section B.3). Direct attachment of trifluoromethyl or perfluoroalkyl groups onto the porphyrin

macrocycle at the /w.ro-positions of porphin (I) (nomenclature, p.viii) ,39,112

38
a n ( j m e

P-positions of ^jo-diarylporphyrinl 18
has been reported, but there are no reports of

P-trifluoromethyl-w^o-tetraarylporphyrin in the literature. As described in chapter I, major

players in the development of P-450 mimics using synthetic porphyrins are

meso tettaarylporphyrins with electron-withdrawing substituents on the p-pyrrolic positions (see

chapter I, section B.2.). Accordingly, the main purpose of this research is to initiate and

investigate the chemistry of p-trifluoromethyl-^j"o-tetraphenylporphyrins. The first part of this

section describes the synthesis of P-tjifluoromethyl-^j'o-porphyrins. The second part describes

the synthesis of p-methyl-^jo-tetraphenylporphyrins. P-Methyl-wwo-tetraphenylporphyrins were

compared with the corresponding P-trifluoromethyl- analogues in order to investigate the

contrasting electronic characteristics of — C H and - C F 3 3 groups; electron-releasing vs. electron-

withdrawing(Table 1-3, p.31). Analysis by comparison may allow the effects of the electron-

withdrawing C F group on the porphyrin macrocycle to be fully assessed. Finally, the synthesis of
3

Zn(II), Co(II), and Fe(III) complexes of P-tetealds(ttifluorometliyl)-OTW<?-tetJ:aphenylporphyrin is

described. These metalloporphyrins were required to investigate the nature of the novel
 65

porphyrins by cyclic voltammetry, spectrophotometric titration, and X-ray crystallography. The

catalytic oxidation of cyclohexane and cyclohexene was subsequently conducted using novel

Fe(III) porphyrins as catalysts.

/. Trifluoromethylation

It has been mentioned that direct introduction of —CF groups onto the P-pyrrolic
3

postions of porphyrins is most easily achieved using Cu(I) assisted trifluoromethylation

(chapter I, section C), which can be classified into two methods; (i) pyrolysis of trifluoromethyl

acetate and (ii) metathesis of tofluoromethylcadniium in the presence of Cu(I) halide. The active

trifluoromethylating reagent is C F C u and iodinated or brominated aromatic compounds are

3

required for both methods (Chapter I, section C.2.). Several proposed mechanisms for copper

assisted nucleophilic substitution of halogenated aromatic compounds have been reviewed in the

literature. 181

The strategy adopted for P-trifluoromethylation is shown in Scheme 2-1.

Metalloporphyrins as starting materials were required in order to prevent formation of the Cu(I)

and Cu(II) complexes by the reaction of the free-base porphyrins with C F C u (even though a 3

free-base porphyrin was tested in a trifluoromethylation by the metathesis method). It has been

reported that the use of iodinated aromatic compounds generally gives higher yields of

trifluoromethyl aromatic compounds than the use of brominated ones for Cu(I) assisted

trifluoromethylation. 133
Accordingly, P-iodo-«?wo-tetraphenylporphyrins would be ideal

substrates for Cu(I) assisted trifluoromethylation but the iodination of porphyrins has proved to

be difficult, presumably due to the large steric bulk of the iodinium cation. ^ Although 18

iodination at the wwo-position of 5,15-diarylporphyrins is k n o w n , 1 8 3

>! 8 4
effective multiple
 66

P-iodination has not been reported. 2

1 8
Consequendy, the precursors chosen were

P-brominated-OTtfj'o-tetraphenylporphyrins, which are much easier to prepare.

CF Cu
3

by pyrolysis
Products

CF Cu 3

by pyrolysis
Products

Products
CF Cu 3

Br Ph by metathesis

M = 2H , Zn(ll), Cu(ll), Ni(ll)

+

S
che
m e 2-1. Trifluoromethylation strategies.

The trifluoromethylation strategies outlined in Scheme 2-1 are described in detail in the

following sections.

a. Synthesis ofprecursors

The precursors chosen for Cu(I) assisted p-trifluoromethylation according to Scheme 2-1

were the readily obtainable CufTPPBr^fJc) (Scheme 2-2), H T P P B r (

4 5a)
, Zn(TPPBr ) (
2 4 5
4b)
, 4

Cu(TPPBr ) (
4
4 5c)
, and Ni(TPPBr ) (45d) 4 (Scheme 2-3). Bromination of 2c (Figure 1-8) and 2a

using N B S gave 7c^ 7

and 45a5,186 ^ yields of 75 - 80 %. The structures of the porphyrin 7c
1
8

and 45a were confirmed by mass spectrometry and N M R spectroscopy. Zn(II), Cu(II), and

Ni(II) complexes of 45a were synthesized by the general porphyrin metallation m e t h o d . 68

This
 67

metal insertion method is conducted in hot D M F in the presence of metal salts and produced the

corresponding metalloporphyrins (45b, 45c, and 45d) with > 90 % yield.

b. Trifluoromethylation by pyrolysis of CFjCO^Na/ Cul

(1) Reaction using CufTPPBrg) (7c)

Scheme 2-2 shows the attempted trifluoromethylation of Cu^TPPBrg) (7c) by pyrolysis of

C F C 0 N a / C u l in D M F . Firstly, trace amount of water in the mixture was removed by the use
3 2

of a. toluene-azeotrope under an atmosphere of N . After toluene was distilled out, the

2

temperature was then raised to 150- 155 °C, and held for 2 h under N . Pyrolysis of C F C 0 N a 2 3 2

was observed indirectly by gas evolution (presumed to be C O ^ for the first 10-15 min from the

point the temperature had reached 150 °C. The reaction was monitored by UV-visible

spectroscopy. The Soret band of the reaction mixture (466 nm for 7c) was observed at 434 nm at

30 min and no other changes were subsequently observed. Thin-layer chromatography (TLC) of

the product mixture (44c) using various combinations of organic solvents and silica-gel plates did

not show a satisfactory separation of the trifluoromethylated Cu(II) complexes (

4 4c)
. Low

resolution EI mass spectrometry of 44c showed tettalds(trifluoromethyl)-^j-o-

tetraphenylporphyrinato Cu(II) (44c (x = 4)) as the major product in 100% intensity.

Compounds 44c (x = 2), 44c (x = 3), 44c (x = 5), and 44c (x = 6) were also detected in 30, 74,

57, and 2 % intensities respectively. N o sign of bromine groups on porphyrins in the reaction

mixture was observed by mass spectrometry. Presumably reductive elimination of halogen had

occurred. 187 A free-base mixture (44b) was obtained when Cu(II) complex 44c was treated with

concentrated H S 0 2 4 and neutralized with 10 % aqueous N a H C 0 . 3 T L C analysis of free-base

mixture 44a showed a better resolution than that observed for the Cu(II) complex mixture 44c

and at least six compounds were observed by T L C analysis. Since the spots on the T L C plate
 68

Ph
44a

TLC

T
More than 6 compounds

S
che
m e 2-2. Trifluoromethylation of P-octabromo-OT^o-tetraphenylporphyrinato Cu(II) (7c)
by pyrolysis of C F C 0 N a / C u I . i)toluene-azeotrope, 120 °C, N
3 2 2 ii)150 - 155 ° C , 2 h, N ,
2

iii)conc. H S 0 , iv)10 % aq. N a H C 0 .

2 4 3
 6
9

smeared and were so close together, isolation of the compounds was not attempted. Evidently,

regioisomers and partially substituted P-tnfluoromethyl-TPPs existed in the mixture. This

preliminary trifluoromethylation using p-octabromo-TPP (7c) led the author to use

P-tetrabromo-TPPs (45b, 45c, and 45d) as precursors in an attempt to effect a cleaner reaction.

(2) Reactions using MTPPBr 4 (M = Zn(II), Cu(II), andNi(II)) (45b,45c,and 45d)

The previous experiment showed that a significant number of partially trifluoromethylated

porphyrins are produced due to reductive dehalogenation of brominated positions, since no

bromine substituents are left after the reaction. A s a result o f this incomplete

trifluoromethylation, various porphyrins, presumably including some regioisomers, are produced.

In order to simplify the reaction, the P-tetrabrominated porphyrins, Zn(TPPBr ) (

4
4 5b)
,

Cu(TPPBr ) (
4 5c
4)
, and Ni(TPPBr ) (45d) (Scheme 2-3) were used. The central metal was varied
4

in order to investigate the effect of metals upon reactivity in trifluoromethylation. The reaction

procedure for trifluoromethylation by the pyrolysis method is as described in Scheme 2-2.

After trifluoromethylation using any of the three metal complexes (45b, 45c, and 45d), the

EI mass spectrum of the product mixture showed three mass peaks corresponding to P-bis-,

P-tris- and P-tetralds(ttifluoromethyl)-^j-o-tettaphenylporphyrins (M(TPP(CF3))(46),

2

M(rPP(CF))(47), M(rPP(CF))(48) (M = Zn(Ii), Cu(II), or Ni(H)) but T L C analysis (silica gel

33 3 4

plate, CHCl /pet. ether) of the product mixture (for any of Zn(II), Cu(II), and Ni(II)) showed
3

smearing of the spots and did not show separation of 46, 47, and 48. Fortunately, it was found

that free-bases (H TPP(CF ) (

24 6a)
, H TPP(CF ) (
3 2 4 7a)
, and H T P P ( C F ) (
2 4 8a)
) can be well
3 3 2 3 4

separated on a preparative silica gel plate. The free-base porphyrins (46a, 47a, and 48a) were thus

isolated, after demetalation of the product mixture, by silica gel chromatography (this statement
 70

MTPPBr 4 (45)

a: M = 2H+

b: M = Zn(ll), c: M = Cu(ll),
d: M = Ni(ll)

CF C0 Na/Cul
3 2

toluene/DMF

i, a

Scheme 2-3. Trifluoromethylation of P-tetrabromo-«?tfJO-porphyrins (45) by pyrolysis of

C F C 0 N a / C u I . ^toluene-azeottope, 120 ° C , N , ii) 150 - 155 ° C , N , 1 h iii)conc. H S 0 ,
3 2 2 2 2 4

iv)10%aq. N a H C 0 3
 71

applies to product mixtures in any complex form of Zn(II), Cu(II), and Ni(II)). Isolated free-base

porphyrins H T P P ( C F ) (
2 4 6a)
, H TPP(CF ) (
3 2 4 7a)
. and H T P P ( C F ) (48a)
2 3 3 2 3 4 were identified by

low resolution E I mass spectrometry, H and 1 1 9

F N M R spectroscopy, and elemental analysis.

Assignment of the N M R spectrum of 46a was difficult because peaks could not be assigned

to a specific structure of H T P P ( C F ) . It is believed that 46a

2 3 2 is a mixture of symmetric

regioisomers, 46a' and 46a", which were not separated by chromatography. The results of

trifluoromethylation of |3-tetrabromo-OTtfjo-tetraphenylporophyrins by pyrolysis of

CF C0 Na/CuI
3 2 are summarized in Table 2-1. The yield of

P-tettalds(trifluoromethyl)porphyrin (48a) by this method was always low, while (3-bis- and

P-tris(tjifluorometiiyl)porphyrins (46a and 47a) were produced as major products in about

20 - 40 % yield. Variation of the central metal did not significantly affect the yields. It seems that

reductive debrornination is dominant in the reaction and this governs the product distribution.

46a' 46a"
Tabl
e 2-1. Results of trifluoromethylation by pyrolysis method . a

Starting
M Solvent Time/h Product (%) b

Material
45b Zn(II) DMF 1 46a(16),47a(29), 48a(2.5)
DMF 24 46a(21), 47a(19), 48a(3)
45c Cu(II) DMF 1 46a(37), 47a(29), 48a (
5 )
45d Ni(H) DMF 1 46a(28),47a(18),48a(3)
a
P o r p h y r i n / C u I / C F C O N a = l / 1 6 / 4 0 . Temp. = 150 °C.
3 2

b
Yields are calculated based on M(TPPBr ) (45). 4
 72

In summary, the yields of the separated P-tettalds^fluoromethyl)-^^-

teteaphenylporphyrin were low by use of the pyrolysis method but isolation of three novel

P-trifluoromemylporphyrins (46a, 47a, and 48a) which are important for analysis of electron-

deficiency of porphyrin macrocycles was allowed by this experiment. Trifluoromethylation by the

pyrolysis method is easy to perform. Specifically, handling of the reagents is facile and the

reagents are not expensive. However, this method requires high temperatures (150 °C) in order

to generate the active C F C u species and thus Cu(I) assisted substitution is hampered by
3

reductive debromination of the starting material. Consequendy, one drawback of this method is

that significant amounts of partially trifluoromethylated porphyrins are produced. Thus,

trifluoromethylation under milder conditions was needed, especially for multiple

trifluoromethylation, in order to avoid unnecessary debromination.

c. Trifluoromethylation by CFfZu generated by the metathesis of trifluoromethylcadmium and CuBr

The active trifluoromethyl agent in Cu(I) assisted trifluoromethylation is C F C u , which is 3

common to both the pyrolysis and metathesis methods. A n important difference between the

two methods concerns the in-situ generation of C F C u . In the pyrolysis method, C F C u is

3 3

generated from C F C O N a
3 z and Cu(I) halide at about 150 °C. O n the other hand, in the

metathesis method, C F C u is generated from trifluoromediylcadmium (mixture of (CF ) Cd and

3 3 2

CF CdBr) and Cu(I) halide at — 40 °C (see chapter I, section C.2.). The low reaction temperature
3

required for the metathesis method enables the trifluoromethylation to be performed under

milder conditions. The reduced temperature prevents reductive dehalogenation.

(1) Preliminary experiments

Trifluoromethylation using H T P P B r
2 4 (
4 5a)
, Zn(TPPBr ) (
4
4 5b)
, Cu(TPPBr ) (
4 5c)
, and 4

Ni(TPPBr ) (45d)
4 with C F C u generated by the metathesis of trifluoromeflrylcadmium and CuBr
3
 73

was examined to assess the effect of the central metal upon reactivity. The reaction is shown in

Scheme 2-4. According to literature precedence,^ 39

m e reaction was conducted at 70 °C for

several hours in D M F using compounds H T P P B r

2 4 (
4 5a)
, Zn(TPPBr ) (
4 5b)
, Cu(TPPBr ) (
4 4 5c)
, 4

and Ni(TPPBr ) 4 (
4 5d)
. Since the work-up procedure is similar for all of the reactions, the

procedure is only described for the reaction with 45b as the starting material. After the reaction,

D M F and some of the H M P A were distilled off under reduced pressure. The green viscous

residue was diluted with acetone and filtered. E I mass spectrometry of the mixture showed that

it contained not only Za(TPV(CF^ (

4 6b)
, ZnCTPP^^) (
4 7b)
, and Zn(TPP(CF ) ) (
4 8b)
, but 3 4

also partially brominated and partially trifluoromethylated products (49b, see Scheme 2-4). The

crude yield of compound mixture 49b was significant (~ 40 % based on 45b). After the mixture

containing compounds 46b —4

9b was treated with cone. H S 0 and neutralized with 10%
2 4

aqueous N a H C 0 , free-bases 46a

3 - 48a were isolated by silica gel chromatography. Free-bases of

49 could not be isolated because the spots were co-eluted, thus appearing as a broad band. The

results are summarized in Table 2-2. The Cu(II) and Ni(II) complexes (45c and 45d) were not

very soluble in D M F at 70 °C and thus trifluoromethylation reactions were unsuccessful; no

tetralds-trifluoromethyl product was obtained and more than 70% of the starting materials was

recovered. Trifluoromethylation using free-base porphyrin (45a) was also unsuccessful. Free-base

porphyrin 45a was metallated with CuBr under the metathesis conditions and Cu(TPPBr ) 4 (45c)

precipitated out of solution and also small amount of C u deposition resulted. Thus,

trifluoromethylation using free-base porphyrin (45a) resulted in a similar product distribution as

was obtained for Cu(II) porphyrin 45c. Zn(II) porphyrin 45b is more soluble than 45c and 45d

in D M F at 70 °C. Thus, Zn(II) porphyrin 45b seems to be the best choice of the four tested

porphyrins. However, even with this 45b as the starting material, 10 % of it was recovered. This

implies that 45b may not be completely soluble under the reaction conditions.
 r
(
y49)

Ph CF 3 Ph

47 48

S
che
m e 2-4. Trifluoromethylation of P-tettabromo-^-fo-porphyrins by metathesis
of CF -Cd*/CuBr/HMPA. i)70 °C, N , 5 h, ii)removal of solvents, iii)filtration,
3 2

iv)conc. H S 0 , v)10 % aq. N a H C 0 * C F - C d = (CF)Cd + C F C d B r .

2 4 3 3 3 2 3
 75

Tabl
e 2-2. Trifluoromethylation by metathesis using M T P P B r (
4 5)
. 4
a

Porphyrin M Product (%) b

45a 2H +
45c(67), 46a(l), 47a(
4 )
, 48a(0)
45b Zn(II) 45b(10), 46a(2), 4 7 a (
8 )
, 48a(l 1)
45c Cu(II) 45c(73), 46a(2), 4 7 a (
5 )
, 48a(0)
45d Ni(II) 45d(86), 46a(l), 47a(2), 48a(0)
a
Porphyrin 0.16 mmol/CuBr 4 m m o l / C F - C d 4 m m o l / H M P A 4 mL,
3

70 °C, 5 h, under N . Isolated yields are reported. Partially brominated and partially
2
b

trifluoromethylated porphyrins are not shown in the table because isolation was not
possible.

P-Tetrakis-trifluoromethyl porphyrin was produced in 11 % yield. This result represents a

significant improvement from that observed in the pyrolysis method. However, the yield was still

low. Since significant amounts of partially brominated and partially trifluoromethylated

porphyrins (49b) were obtained, the reaction may be slow and long reaction times may be

needed. Usually, trifluoromethylation of halogenated aromatic compounds by metathesis under

the same reaction conditions gives moderate yields (e.g. 76 % for the conversion of

on^o-iodotoluene to on$o-tjifluoromethyltoluene)133 j n thi s W O rk, trifluoromethylation is

required to occur in a sterically hindered region (P-pyrrolic positions are located between two

phenyl groups and adjacent to each other) and the reaction may thus be slower than usual

trifluoromethylation using simple substrates such as iodotoluene. Consequendy, either longer

reaction times or higher reaction temperatures may be necessary in order to facilitate

trifluoromethylation with the same molar ratio of the reactants. Thus, optimization using

Zn(TPPBr ) (45b)
4 in metathesis induced trifluoromethylation at different reaction times and

temperatures was investigated.

 76

(2) Optimisation of theyieldfor B4etrakis(trifluoromethyl)-meso-tetraphenylporphyrin

As described in the previous section, trifluoromethylation of Zn(TPPBr ) (45b) 4 under the

conditions shown in Scheme 2-4 showed significant amounts of partially brominated and

tnfluoromethylated porphyrins, presumably due to steric hindrance. The first part of this section

describes investigations concerning the effects of reaction times upon the yield of

P-tettakis(tiifluoromemyl)-OTWo-tetJraphenylporphyrin by the metathesis methodology.

The reaction time was extended to 88 h with all other reaction conditions shown in

Scheme 2-4 remaining constant. During the reaction, changes in the UV-visible spectrum were

monitored. As shown in Figure 2-1, the spectrum of an aliquot of the reaction mixture diluted in

C H C 1 changed considerably with time. The Soret band (430 nm) of 48b
2 2 (trace A in Figure 2-1)

had shifted to 448 nm and a maximum of a broad Q band was at about 700 nm after

4 h (trace C). After 48 h, the Soret and the maximum of the broad Q band was seen to have

gradually blue-shifted and settled at 438 nm and 660 nm, respectively (trace F). There was a large

shoulder around 460 nm. There was no change after 48 h (trace F (48 h), G (68 h), and

H (88 h)). Trace I in Figure 2-1 is the spectrum of the required product Zn(TPP(CF))(48b) in 34

CH Cl2 and trace J is 48b

2 in CHjCL^ containing ~1 % (v/v) H M P A . Spectrum J has maxima at

448 nm and 724 nm, with a large broad shoulder at 462 nm, which is attributed to the presence

of H M P A by comparison to the spectrum F, G, and H. After 88 h, the reaction mixture was

subjected to an acidic work-up (TFA-CH^CL) to effect demetallation of the products. Analysis

by F A B mass spectrometry indicated that the product mixture contained several

perfluoroalkylporphyrins as shown in Table 2-3. The mass of compound 50a is different from

that of H T P P ( C F ) (47a)
2 3 3 by 50, which agrees with the mass of - C F - (= 50.0). It is conjectured
2

that the presence of compounds 50a, 51a, 52a, 53a, 54a, and 55a originates from the
 77

00

CO

T 1 1 1 r

350 400 450 500 550 600 650 700 750 800
Wavelength/nm

F i
g u re 2-1. UV-visible spectra during trifluoromethylation of 45b at 70 °C.
A: 45b, B: 15 min, C: 4 h, D: 20 h, E: 25 h, F: 48 h, G: 68 h, H: 88 h,
I: 48b, J: 48b + HMPA..
 78

introduction of extended perfluoroalkyl chains into the porphyrin (see eq.(1.3) and (1.4), p.37).

Similarly, a mass difference of 50 is seen among 48a, 52a, 54a, and 55a and between 50a and

51a. The structure of 52a is shown below but the regiochemistry of porphyrins 50a, 51a, 53a,

54a, and 55a is uncertain.

Tabl
e 2-3. Products obtained by the reaction at 70 °C for 88 h
Products Mass(obsd) a)
Mass(calcd for) Relative Intensity
H TPP(CF )
2 3 3 (47a)
820 818.7(C H F N )
47 27 9 4 24
H TPP(CF )
2 (48a)
3 4
888 886.7(C H F N )
48 26 12 4 80
50a 870 868.8(C H F N )
48 27 n 4 37
51a 920 918.8(C H F N )
49 27 13 4 36
H TPP(CF CF )(CF )
2 2 3 (52a)
3 3938 936.8(C H F N )
49 26 14 4 100
53a 970 968.8(C H F N )
50 27 15 4 21
54a 988 986.8(C H F N )
50 26 16 4 81
55a 1038 1036.8(C H F N ) 51 26 18 4 21
Low resolution F A B mass spectrometry.

Separation of the perfluoroalkylated porphyrins was attempted. A patient and agonizing

search for a suitable solvent system for T L C analysis found a solvent system to separate these

porphyrins as shown in Table 2-4. The major products 48a, 52a, and 54a could be separated on

a silica gel chromatographic plate using benzene/cyclohexane/acetone= 6/3.5/0.5 (Table 2-4).

Due to the small amounts present, products 50a, 51a, 53a, and 55a could not be clearly seen on

the T L C plate. After 48a and 52a were isolated, a weakly colored (orange) band was left near the

top of the column. This colored band could not be flushed out with polar solvents such as

M e O H or acetone. Unfortunately, 54a could not be isolated. Presumably, it decomposed on the

 79

silica gel column during the chromatographic separation of 48a and 52a. Isolated 48a and 52a

were identified by ' H and F N M R spectroscopy, E I mass spectrometry, and elemental analysis.
1 9

Tabl
e 2-4. R values for metal-free perfluoroalkylated porphyrins
f

Solvent System
CH Cl :hexane
2 2 C H :cyclohexane:acetone
6 6

=3:7 =6:3.5:0.5
Porphyrin

46a 0.57 a)
-

47a 0.29 -

48a 0.09 0.38

52a 0.09 0.27
54a 0.09 0.18 b)

a)
Mixture of regioisomers. b)
Smears.

The yield of the required porphyrin H T P P ( C F ) (48a) 2 3 4 was 13 % (Table 2-5). This result

was similar to that obtained by trifluoromethylation at 70 °C and 5 h (see Table 2-2) but the yield

of H T P P ( C F C F ) ( C F ) (52a)
2 2 3 3 3 was 22 % (Table 2-5). This product was not obtained after the

reaction of 5 h duration. Since partially brominated and partially trifluoromethylated porphyrins

were not detected in the product mixture by F A B mass spectrometry, the reaction time (88 h)

was evidently long enough to allow complete exchange of the bromine by nucleophiles.

However, it seems that exchange of - B r and —CF groups is slow and the C F 3 3 nucleophile is

lost due to extension of perfluoroalkyl anions (eq.(1.3) and (1.4), p.37). Thus, nucleophilic attack

by oligomerized perfluoroalkyl anions rather than the trifluoromethyl anion is increased, giving

porphyrins with oligomerized perfluoroalkyl groups.

In summary, extension of the reaction time to 70 °C facilitated exchange of - B r with

perfluoroalkyl groups but the product distribution was found to be complex due to extension of

the perfluoroalkyl chain. 133 Separation and purification of the complex mixture of
 80

P-trifluoroalkylated porphyrin products were found to be extremely difficult and not wholly

successful despite intense efforts.

Reactions were also run at higher temperatures in order to investigate the effect of

temperature on the product distribution and yield.

Figure 2-2 shows the UV-visible spectra observed for trifluoromethylation at 110 °C under

otherwise identical conditions to those shown in Table 2-2. In this reaction, the peak of the Soret

band of 45b was observed at 448 nm at 15 min (trace B). The spectra remained unchanged

between l h (C) and 2 h (D). A t 4 h (E), a split of the Soret band was observed. A t 6 h (F), the

Soret was a single band at 434 nm and there was little change in the spectra afterwards (8h (G)

and 21 h (H)). Unlike the case for the reaction at 70 °C, the shoulder around 460 nm is not

prominent after reaction completion (compare Figure 2-1, H to Figure 2-2, H). The final

position of the Soret band was 4 nm shorter than that of the reaction at 70 °C and the final U V -

visible spectrum seems quite different to traces I and J. E I mass spectrometry of the final

reaction mixture contained neither partially brominated porphyrins nor the porphyrins with

extended perfluoroalkyl chains. The product mixture contained only bis-, tris-, and tetrakis-

trifluoromethyl Zn(II) porphyrins (46b, 47b, and 48b). After demetallation, the porphyrin

mixture was purified by column chromatography on silica gel to give the isolated products

H T P P ( C F ) (46a)
2 3 2 (13 %), H T P P ( C F ) (47a)
2 3 3 (12 %), and H T P P ( C F ) (48a)
2 3 4 (17 %).

Dehalogenation of halogenated aromatic compounds in D M F is known. 187

The reaction was also run at 90 °C and isolation of the final products in free-base form

was performed. Isolated products of the several reactions with different temperatures and times

are summarized in Table 2-5.

F i
g u re 2-2. UV-visible spectra during trifluoromethylation of 45b at 110 °C.
A: 45b, B: 15 min, C: 1 h, D: 2 h, E: 4 h, F: 6 h, G: 8 h, H: 21 h, I: 48b,
J: 48b + HMPA.
 82

At low reaction temperatures, extension of perfluoroalkyl chains occurs giving significant

amounts of H T P P ( C F ) ( C F C F ) (
2 3 3 522a)
. A t high reaction temperatures the yields of P-bis- and
3

P-teis(trifluorometliyl)porphyrin (46a and 47a) increase and 52a is not isolated. As shown in

Table 2-5, the several-hour reactions at 90 °C resulted in the best yields of the required

P-tetrakis(difluoromethyl)porphyrin (
4 8a)
.

Tabl
e 2-5. Isolated P-perfluoroalkyl-^gJo-tetraphenylporphyrins.
Isolated porphyrin(%)
Temp.(°C) Time (h)
46a 47a 48a 52a
70 88 5.6 13 22
90 7 9 21 38 10
5 11 24 42 8
110 21 13 12 17
8 16 13 20

In summary, the pyrolysis method was not appropriate for the effective

trifluoromethylation of P-octabromo- and P-tetrabromo-/»wo-tetraphenylporphyrins. Only

complex mixtures and low yields of P-tiifluoromemyl-w^o-tettaphenylporphyrins were obtained

using P-octabromo-w^-tetraphenylporphyrin as a starting material. The reactions using

P-tetrabromo metalloporphyrins yielded P~bis- or P-tris (trifluoromethyl) -meso-

tetraphenylporphyrins as major products and P-tettalds(tjifluoromethyl)porphyrin was obtained

in very low yields. The reaction conditions, especially the high temperature (150 °C), were found

to be too severe for multiple trifluoromethylation using P-octabromo or P-tetrabromoporphyrins

and reductive debromination seemed to dominate under these conditions.

Trifluoromethylation by C F C u generated by the metathesis of tofluoromethylcadrnium

3

and CuBr can be performed under relatively milder reaction conditions. However, the highest
 83

temperature reported for this reaction (70 °C)133 as not sufficiently high for effective multiple
W

trifluoromethylation of p-tettabromo-wwo-tetjraphenylporphyrins. Longer reaction times at 70 °C

increased the yields of higher fluorinated alkyl species, which attack the brominated p-pyrrolic

positions to yield porphyrins with extended perfluoroalkyl chains such as 50a - 55a. Reactions at

110 °C did not give such porphyrins but higher yields of porphyrins 46 and 47 were obtained due

to reductive debromination. Thus, the yields of P-tettalds(ttifluoromethyl)porphyrin 48 were

maximized for the reaction at 90 °C for 5 h.

The UV-visible spectra obtained during trifluoromethylation via the metathesis method

showed significant red-shifts of the peaks in the early stage of the reactions (Figure 2-1 and

Figure 2-2), and for the reaction at 110 °C red-shifts were followed by blue-shifts of the peaks

(Figure 2-2). It is known that porphyrin plane distortion induces red-shifts of UV/visible

absorption bands (see Chapter 1, section D./.b.).144-147 Steric interaction between the adjacent

pyrrolic P-substituents was analyzed by computer modeling. Figure 2-3 shows geometry

optimized 3,4-dibromopyrrole and 3,4-bis(trifluoromethyl)pyrrole (2,5-hydrogens were omitted)

by molecular mechanics.188 According to the calculation, the —C F 3 groups are closer to the

pyrrole ring than the —Br groups and the van der Waals radius of —CF is much larger than that
3

of —Br. The distance between the two —Br centers (3.645 A) is comparable to the sum of the two

- B r vdw radii (3.90 A). O n the other hand, the C - C distance between the two - C F 3 groups

(3.273 A) is much smaller than the sum of the two - C F vdW radii (5.66 A). Since rotation of the
3

—CF presumably occurs, steric interaction between the two —CF groups may be seriously large.
3 3

Keeping this in mind, the author attempted to rationalize the unique shifts of peaks of the U V -

visible spectra during trifluoromethylation (Scheme 2-5). In the early stage of the reactions, the

partially brominated and trifluoromethylated porphyrins such as mono-trifluoromethylated

 84

v d W ( B r ) = 1.95 A

C - F = 1.492 A
v d W ( F ) = 1.35 A
. w d W (CF3) = 2.83 A

Fi
g ur
e 2-3. 3 , 4 - D i b r o m o p y r r o l e and 3,4-bis(trifluoromethyl)pyrrole
m o d e l e d by H y p e r C h e m . 1 8 9
T h e van der Waals (vdW) radii o f B r and F were
obtained f r o m ref.123 and the v d W o f C F was calculated f r o m the C - F b o n d
3

length and the v d W (F).

8
5
 86

ZnTPPBr (CF ) or bis-tofluoromethylated Z n T P P B r ( C F ) may be produced fairly easily but

3 3 2 3 2

introduction of the bulky - C F groups presumably forces the macrocycle to distort to some
3

degree. Macrocycle distortion will cause red-shifts of the absorption bands in the UV-visible

spectrum. 144-147 j j conjectured that a problem starts after introduction of the second —CF
t s 3

group. Since the steric interaction between the adjacent - C F groups on a pyrrole is severe as
3

shown in Figure 2-3, introduction of the third and the fourth - C F should be much more
3

difficult (slower) than that of the first two. The measures taken in order to overcome this steric

encumberance were to extend the reaction time and to raise the reaction temperature. For

extended reaction times at 70 °C, more of the extended perfluoroalkyl chains are introduced onto

the porphyrins and complete trifluoromethylation is hampered by extension of perfluoroalkyl

chain. O n the other hand, at 110 °C reductive debromination prevents effective

trifluoromethylation. The reactions at 90 °C gave the best yield (-40%) of Zn(TPP(CF ) ) 3 4 (48b)

of the three temperatures. However, difficult chromatographic purification was still required in

order to obtain pure P-tetraltis(rjifluorometliyl)-OTtfj'o-teteaphenylporphyrin (

4 8a)
. Nevertheless,

the optimized trifluoromethylation reaction produces the required porphyrin 48a in a sufficient

yield to continue further studies. The yield of required 48a could also be improved by increasing

the amount and concentration of C F C u but the effect of molar ratio of the reactant on the
3

product yield was not investigated.

In the demetallation process following trifluoromethylation, CuBr must be completely

removed. This is because treatment of the product mixtures containing 48a with acid in the

presence of CuBr gives an unidentified orange compound. A s shown in Figure 2-4, a broad

Soret-band-like peak appeared at 420 nm and no Q bands were observed in the UV-visible

spectrum of this orange compound. This phenomenon was checked with pure 48a in the
 350 450 550 650 750 850 950
Wavelength (nm)

Fi
g ur
e 2-4. UV-visible spectra of the orange compound (dark line) and
HTPP(CF)(48a) (narrow line).
2 34
 88

presence of CuBr in acidic (TFA) C H C 1 and indeed the orange compound was obtained.
2 2

Porphyrin 48a seems to be reduced to the orange compound by the electron produced by the

presence of CuBr in acidic conditions, thus causing a significant decrease of the final product

yield. This phenomenon was also observed with H T P P ( C F C F ) ( C F ) (

2 5 2a)
. This phenomenon
2 3 3 3

can be avoided by careful removal of CuBr (for example tofluoromemylporphyrins in metallated

forms are very soluble in acetone, CH C1 , or CHC1 but CuBr is not. Thus after the reaction,
2 2 3

dried product mixtures were dissolved in acetone and CuBr could be filtered off before

demetallation. Although further investigation to study the mechanism of reduction was not

attempted since the orange compound could not be identified, sensitivity of these porphyrins to

reducing reagents will also be shown in section AJ. and B.5.a.(2).

2. Methylation

(3-Methyl-wwo-tetraphenylporphyrins were required in order to compare the electronic and

structural effects of these porphyrins with the trifluoromethyl analogues. Methylation of

P-tettabromo-^j-o-tettaphenylporphyrin Zn(II) complex (45b) was performed by Cu(I) assisted

methylation involving the use of C H L i and Cu(I) halide. 1^9 As shown in Scheme 2-6, 45b
3 was

treated with an excess of Li(CH ) Cu at 32 - 33 °C for 24 h, which was formed by the reaction of
3 2

C H L i and CuBr at - 80 °C in ether. Oligomerization as observed for trifluoromethylation of

3

P-tetrabromoporphyrin by metathesis did not occur in this case. After the coupling reaction, the

remaining bromo substituents were removed by reflux in D M F in the presence of CuBr under

air for 2 h. Since the major purpose was to obtain P-methylporphyrins but not to analyze the

methylation reaction products, brominated sites were eliminated in order to simplify separation

of P-methylporphyrins. Formation of p-methyl-^jo-tetraphenylporphyrins (57b - 59b) was

confirmed by EI mass spectrometry. The solubility of the Zn(II) complexes of

 ZnTPP (2b) 58b 59b

iii, iv

T
2a (32 %), 56a (0.5 %), 57a (19 %), 58a (17 %), 59a (15 %)

S
che
m e 2-6. Methylation of 45b. i) E t 0 , 32 ° C , 24 h, ii)CuBr, D M F , reflux, 2 h,
2

iii)TFA, reflux, 1.5 h, iv)10 % aq. N a H C 0 . a = 2 H , b = Zn(II)

3
+
 90

p-methylporphyrins (ZnTPP(CH ) (
5 7b)
, ZnTPP(CH ) (
5 8b)
, ZnTPP(CH ) (
59b)
) was low in
3 2 3 3 3 4

CHC1 , C H C 1 and benzene, while the free-bases showed moderate solubility in those solvents.
3 2 2

Thus, separation by chromatography on silica gel was performed with the metal-free porphyrins

(H TPP(CH ) (
2 5 7a)
, H TPP(CH ) (
3 5 8
2a)
, H TPP(CH ) (
5 9a)
)
. The isolated yields are shown in
2 3 3 2 3 4

Scheme 2-6. p-Mono(methyl)-w^-tetraphenylporphyrin (H TPP(CH )) (56a) 2 3 and H T P P

2 (2a)

were also obtained in 0.5 % and 32 % yield, respectively. As found for trifluoromethylation

products, P-bis(methyl)-OTtfj-o-tetraphenylporphyrin (57a) is formed as a mixture of regioisomers

which were not separated.

In summary, methylation of the P-tetrabromo-wwo-tetraphenylporphyrin zinc complex by

CH Li 3 and CuBr (Li(CH ) Cu)

3 2 was achieved. The required P-tetramethyl-w^o-

tetraphenylporphyrins (59a) were obtained in 15 % yield. The yield was low but since the

amount of isolated 59a was sufficient for analysis to compare with P-tetrakis(trifluoromethyl)-

OTtfjo-tetraphenylporphyrin (
4 8a)
, this reaction was not optimized. Two other P-methyl

porphyrins (57a and 58a) were also obtained, which enabled a study of a series of compounds.

3. Metallation

MetaUation of H T P P ( C F ) (48a) 2 3 4 with Zn(H)/Co(H)/Fe(Iir) is described to give the

corresponding complexes. The Zn(II) and Co(II) complexes were to be used in electrochemical

studies and in the study of axial ligand binding by spectrophotometric titration.

Zn(TPP(CF ) ) (48b) 3 4 was synthesized by trifluoromethylation of Zn(TPPBr ) (45b) 4 as described

in the previous section. However, pure p-tettalds(trifluorometJiyl)-OTtfj"o-tetJ:aphenylporphyrin

could only be obtained by chromatography of the free-base 48a. Thus, complex 48b was

subsequently obtained by re-metallation of 48a. The Fe(III) complex is important for models for
 91

cytochromes P-450s since the enzymes contain protoporphyrin I X Fe(III) complex in the

functional site.

a. Synthesis of Zn(II) and Co(II) complex of 48

Insertion of Zn(II) and Co(II) into 48a was found to be straightforward. As shown in

Scheme 2-7, 2.5-3 eq. (excess amount of metal salts were used to ensure complete metallation) of

CF 3 Ph

MTPP(CF ) 3 4

98 %, 48b: M = Zn(ll)
96 %, 48e: M = Co(ll)

S
che
m e 2-7. Insertion of Zn(II) and Co(II) into H TPP(CF )
2 3 4 (
4 8a)
.
i)Zn(OAc) .2H 0 or C o C l , M e O H - C H C l ,
2 2 2

a solution of Z n ( O A c ) - 2 H 0 (or CoCL) dissolved in M e O H were added to a CHC1 solution of

2 2 3

free-base porphyrin (
4 8a)
. For the reaction with the Zn(II) salt, the color of the brown

suspension of the free-base porphyrin instantly changed to bright green at room temperature

upon addition of Zn(OAc) dissolved in M e O H . The color change was easily observed by U V -
2

visible spectroscopy (UV-visible spectra will be shown later in this chapter). For the reaction

with the Co(II) salt, formation of the complex was observed by a color change from brown to

bright green upon heating the mixture on a steam bath. Since the ligand was known to be pure,

purification required only removal of excess metal salts which was easily done by washing the

CHC1 solution of the complexes with water and drying over anhydrous N a S 0 . The yields for
3 2 4
 92

48b and 48e were 98 and 96 %, respectively. Formation of 48b and 48e was confirmed by

elemental analysis, mass spectrometry, and H and F N M R spectroscopy. J 1 9

b. Synthesis ofFe(III) complexes of 48 and 52

Usually, Fe(III) complexes of porphyrins are made by insertion of Fe(II) into the

macrocycle followed by aerobic autoxidation of Fe(II) to Fe(III). 69

Typically the reactions are

conducted using FeBr i9o 2 or FeCl i9i

2 in dry T H F , F e S 0 - 7 H 0
4 2 (saturated aqueous

solution)69,163 m a c e u c acid/pyridine, or Fe(OAc) (Fe powder in hot acetic acid)

2
69
in acetic

acid. The insertion reaction must be initially performed under A r or N , followed by exposure of 2

the reaction mixture to air after the Fe(II) insertion, thus allowing oxidation to Fe(III). In some

cases Fe(0) (from Fe(CO) ) can also be inserted to give Fe(III) complexes.I ,192
5
63

As shown in path A of Scheme 2-8(a), all of these routes were attempted but synthesis of

the Fe(III) complex of 48a proved to be unsuccessful. In each case when the free-base

porphyrin (48a) was mixed with the Fe(II) or Fe(0) reagent, the solution (initially brown due to

free base 48a) became orange, and showed a broad single band at 418-420 nm in the UV-visible

spectrum in CH C1 . This spectrum was identical to the one obtained from 48a
2 2 + CuBr under

acidic conditions (chapter 2 section A . / . , Figure 2-4). The same spectrum was obtained when the

free-base (48a) was treated with aqueous L-ascorbic acid (we employed this reducing reagent

since ascorbic acid is a well-known reducing reagent for the reduction of transition metal cations

such as Fe(III)l ). Assuming that the orange compound was a reduced form of the free-
93

base 48a by reaction with Fe(0), Fe(II), ascorbic acid, or Cu(I), the orange compound was treated

with an oxidizing reagent such as dilute H O (5-10 %) in C H C 1 but the UV-visible spectrum of
2 2 2 2

the orange compound did not return to that of the free-base. Thus, it was found that 48a is very
 93

Orange c o m p o u n d

Ph Br

(b) Ph-< /FeOIIJ^-Ph

S
che
m e 2-8. Synthesis o f F e C T P P ( C F ) ) C l (48f) 3 4 and F e ( T P P B r ) C l
4 (
4 5e)
.
i ) F e C l , T H F , reflux, 2 h(Ar), 2 h(air); F e , H O A c , 1 0 0 ° C , 2 h(Ar), 2 h(air); or
2

F e ( C O ) , 1 , 6 0 ° C , 5 h(Ar),rt, 12 h(air), i i ) L i N ( S i M e ) , T H F , r.L, A r , i i i ) F e C l ,

5 2 3 2 2

5 0 ° C , 5 m i n ( A r ) , r.t., 2 h(air), iv)neutral alumina c h r o m a t o g r a p h y - C H C l , v)6

3

M aq. H C 1 , v i ) T H F - 2 0 % aq. K O H , r.t, 2 h, air.

 94

sensitive to reduction to give an unidentified orange compound which is not itself easily

oxidized. For comparative purpose, a Fe(III) complex was prepared using H T P P B r (45a) 2 4 but

the free-base 45a did not suffer reduction under these conditions.

In order to facilitate the insertion of Fe(II), and avoid the irreversible reduction of 48a,

path B of Scheme 2-8(a) was followed; firstly the N - H protons of the free-base were

deprotonated by treatment with lithium bis(tjtimethylsilyl)amide (LiN(SiMe ) ) to yield the lithium 3 2

complex of the porphyrin (60), 1 9 4

then this was reacted with F e C ^ . ^ 3
This method

successfully gave the final product, Fe(TPP(CF ) )Cl 3 4 (

4 8f
), in 56 % yield after purification. The

rationale for why reduction of the porphyrin did not occur in this case is probably due to a

change of the reduction potential of the macrocycle by replacement of H +

with L i . The first +

ionization energies of H and I i are 13.60 eV and 5.32 eV respectively,! ^ 9

anc j^ u s H +
should be

more electron-withdrawing than L i and the reduction potential of the macrocycle should
+

decrease (harder to reduce) by replacement of H with L i . In the purification process (step iv in

+ +

Scheme 2-8(a)), the p-oxo dimer (61) was formed on the neutral alumina chromatographic

column. The p-oxo dimer was then converted to 48f by washing 61 in C H C 1 with 6 M HC1.
2 2

Compound 61 can also be produced by treatment of 48f with an alkali solution (step vi in

Scheme 2-8(a). Similarly, Fe(TPP(CF ) (CF CF ))Cl (52c) 3 3 2 3 (not shown in Scheme 2-8) was

obtained in 76 % yield after purification. As shown in Scheme 2-8(b), for 45a, in addition to the

reported F e C l / T H F method^ !,
2
9
Fe(OAc) in 2 acetic acid also worked well to prepare

Fe(TPPBr )Cl (45e)

4 in 92 % yield. Compounds 48f, 52c, and 61 were characterized using E I

mass spectrometry and ' H and F N M R spectroscopy. The ' H N M R spectrum of 48f
1 9
and 52c

showed a broad singlet at 77 ppm and a broad multiplet at 74 ppm respectively, which are similar

chemical shifts to that of 74 ppm observed for the P-pyrrolic protons of Fe(TPPBr )Cl (45e) 4 and
 95

that of 79 ppm observed for Fe(TPP)Cl (2d). These large downfield chemical shifts of the

P-pyrrolic protons are indicative of high spin (S=5/2) Fe(III) porphyrins.191,196

Thus, with compounds Fe(TPP(CF ) )Cl (48f) 3 4 and Fe(TPP(CF ) (CF CF ))Cl (52c)
3 3 2 3 in hand

analysis and comparison studies could be continued.

4. Summary

T o conclude, P-trifluoromethyl and P-methyl porphyrins have been prepared from

p-tetrabromo-porphyrin. Zn(TPP(CF ) ) (48b)

3 4 and Co(TPP(CF ) ) (
3 4 8
4e)
. Preparation of the

Fe(III) complex of P-tetrakis(trifluoromethyl)- and P-tiis(tjifluoromemyl)(pentafluoroethyl)-

porphyrins was found to be more problematic, but eventually Fe(TPP(CF ) )Cl (48f) 3 4 and

Fe(TPP(CF ) (CF CF ))Cl (52c)

3 3 2 3 could be obtained in moderate yields.

Further research into the synthesis of these compounds must focus on increasing the

yields. For the trifluoromethylation reaction, the effect of molar ratio of the reactants may be

investigated. For methylation, palladium-catalyzed cross coupling reaction may be a useful

alternative method.197,198 phe yield of the Fe(III) complex of P-tetrakis(trifluoromethyl)-

porphyrin (481) may be improved indirecdy by understanding the mechanism of reduction of the

free-base porphyrin, which was the major problem in preparation of the complex.

B. Anal
y si
s of P-
t
ri
f
l
u or
o met
h yl
-
w eso-
t
e t
raphenyl
p or
p hyr
i
n s

As described in Chapter I, the porphyrin macrocycle shows characteristic UV-visible,

N M R spectroscopic, and redox properties due to the 7t-conjugated electron system. The strong

electron-withdrawing effect of the —CF group introduced onto the macrocycle affects the
3

electronic property of the macrocycle. Thus, the first point of investigation is the electronic
 96

structures of the novel P-teifluoromethylporphyrins. One of the main objects of section B is to

describe the investigation regarding this point by the UV-visible, N M R spectroscopy, cyclic

voltammetry, and X-ray crystallography.

Since —CF is also a bulky group, the second point of investigation is a structural change of
3

the macrocycle imposed by introduction of —CF groups. In order to achieve this goal the steric
3

effect of -CF 3 groups on the macrocycle, the X-ray crystal structure of a

p-tettakis(trifluoromethyl)porphyrinato Zn(II) (Zn(TPP(CF ) ) 3 4 (

4 8b)
, see Scheme 2-7) is

examined and compared with those of a P-tetramethylporphyrinato Zn(II)

(Zn(TPP(CH ) ) 3 4 (
5 9b)
, Scheme 2-6), a p-tetrabromoporphyrinato Zn(II) (Zn(TPPBr ) 4 (
4 5b)
,

Scheme 2-1), and other reported metalloporphyrins such as Zn(TPP) (2b) (Figure 1-8).

Rationalization of characteristic UV-visible and N M R spectra of P-trifluoromethylporphyrins in

terms of the steric effect as well as the electronic effect of —CF was also attempted. 3

Our tliird point of investigation is the electron-deficiency of the novel

P-trifluoromethylporphyrins. Electron-deficiency and affinity can be discussed in terms of the

redox properties of the macrocycles, although the pure electronic effect of substituents can be

hampered by a structural change of the macrocycle as discussed in Chapter I, section D . Z b .

Accordingly, in order to assess the electron-deficiency of P-tetrakis(tri.fluoromethyl)porphyrin

from view points other than the macrocycle redox properties, determination of the piC, for the

first deprotonation of pyrrolic N - H of p-tettalds(trifluoromethyl)porphyrin and determination of

the stability constants for pyridine and imidazole binding to the central Co(II) of

p-tettalds(tiifluoromethyl)porphyrin Co(II) complex by spectrophotometric titration were

performed. The reason that Co(II) complex was chosen as the porphyrin system and pyridine
 97

and imidazole as ligands is that homologous systems have been studied using a few electron-

deficient porphyrins. The resulting evaluation of electron-deficiency of

P-tettakis(tofluoromemyl)-porphyrin can be easily done by comparing this system with other

reported electron-deficient porphyrin systems.

Details of the analysis are described in the following sections.

/. UV-visible spectra of synthesized novelporphyrins

The main purpose of this section is to analyze the electton-withdrawing effect of

trifluoromethyl groups on the electronic structure of the novel p-trifluoromethyl-w^o-

tettaphenylporphyrins. The three synthetic porphyrins, P-bis-, tris-,

tetrakis(trifluoromethyl)porphyrins (H TPP(CF ) (
2 4 6a)
,
3 2 H TPP(CF ) (
2 4 7a)
, 3 3 and

H T P P ( C F ) (48a)
2 3 4 see Chapter II, section A) are the subject of the investigation. The first part

of this section concerns the UV-visible spectra of the novel P-trifluoromethylporphyrins in the

free-base form. The UV-visible spectra of these are compared with those of

H T P P (2a) (Figure 1-8),

2 H T P P B r (45a)(Scheme 2-1),
2 4 and P-methylporphyrins (
56a
-59
a)

(Scheme 2-6) and the similarity of the spectra of H T P P ( C F ) (

4 7a)
, H T P P ( C F ) (48a)
2 3 3 2 3 4 and

p-tris(trifluoromethyl)(pentafluoroethyl)porphyrin (H TPP(CF ) (CF CF ) (

5 2a)
, p.78) to that of
2 3 3 2 3

bacteriochlorin (64) (p. 108) is to be discussed. The second part of the section describes the

concentration effect on the UV-visible spectral change of H T P P ( C F ) (48a)

2 3 4 and

H TPP(CF ) (CF CF ) (
2 3 5
3 2a)
, since there is a concern that electron-deficient porphyrins may have
2 3

high tendency to aggregate (see Chapter I, section D J.b.).

In the second part of the section the UV-visible spectra of the Zn(II), Co(II), and Fe(III)

P-tettakis(trifluoromethyl)porphyrins are compared with known metalloporphyrins and the some

 98

tendencies commonly observed through the novel P-tettakis(trifluoromemyl)metaUoporphyrins

are described.

a. Free-base porphyrins

(1) UV-visible spectra in CH Cl 2 2

In this section UV-visible spectra of the free-base porphyrins in one of the most common

solvents for porphyrins, CH C1 , are shown and effects of - C F groups on the electronic and
2 2 3

steric properties of the porphyrin macrocycle are discussed.

UV-visible absorption maxima of free-base P-substituted ^j-o-tetraphenylporphyrins

together with reported electron-deficient porphyrins are summarized in Table 2-6. All porphyrins

except for H ( C F ) P (16a,

2 3 4 n=l) (Figure 1-8, p. 11) are «?«o-tetraphenylporphyrins. As observed

along with introduction of other electron-withdrawing groups onto H T P P (2a) 2 (Figure 1-8) (e.g.

2a -> H T P P B r (45a)(Scheme 2-1) or 2a

2 4 H T P P ( C N ) (32a,
2 4 x=4) (Figure 1-20, p.51)),
1
85

large red-shifts of absorption maxima were observed for the series of

p-trifluoromethylporphyrins H TPP(CF )
2 3 2 (
4 6a)
, H TPP(CF ) (
4 7
2a)
, H TPP(CF ) 3 3 2 3 4 (48a)

(Scheme 2-2) and H T P P ( C F ) , ( C F C F )

2 3 2 3 (52a) (
p .
7 8)
. O n the other hand, the series of

P-methylporphyrins H TPP(CH )
2 3 2 (
5 7a)
, H TPP(CH ) (
5
2 8a)
, and 3 3 H TPP(CH )
2 3 4 (59a)

(Scheme 2-6) showed insignificant red-shifts from that of H T P P (2a). 2 These observations

indicate that the electronic structures of P-tjrifluoromethylporphyrins were significantly changed

from that of 2a but those of P-methylporphyrins were not. Interestingly,

OTWO-tettalds(tofluoromemyl)porphyrin39 (H (CF ) P (16a, 2 3 4 n=l)) (Figure 1-12, p.29) shows blue-

shifts of the Soret and of the two of the four Q bands in spite of having four - C F groups. Thus, 3
 99

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 100

the positions of electton-withdrawing groups or the symmetry of the porphyrin and strong

electron-withdrawal of the substituents affect the electronic structure of the macrocycle. U V -

visible spectra of H T P P ( C F )
2 3 2 (
4 6a)
, H TPP(CF ) (
2 4 7a)
, and H T P P ( C F ) (48a)
3 3 2 3 4 in C H C 1 at
2 2

room temperature are shown in Figure 2-5. For comparison, UV-visible spectra of

H TPPBr
2 4 (45a) and (3-methylporphyrins (H TPP(CH )
2 3 2 (
5 7a)
, H TPP(CH ) (
2 5 8a)
, 3 3

H TPP(CH )
2 3 4 (
5 9a)
) are shown in Figure 2-6 and Figure 2-7 respectively (also see Figure 1-14,

p.39 for the spectrum of H T P P 2 (

2 a)
). The spectral pattern observed for H T P P ( C F , ) (46a)
2 2 is

very similar to that of H T P P B r 2 4 (

4 5a)
. This is reasonable from the view point of the inductive

effect of the B-substituents; the inductive effect of four - B r groups (4a = 0.92)(see Table 1-3, p

p.31) is approximately the same as that of two - C F groups (2a = 1.08). The spectral pattern of
3 p

the P-methylporphyrins (Figure 2-7) shows little change from that of Ff TPP (2a) 2 (Figure 1-14),

indicating that P-methylporphyrins have similar electronic structures to that of 2a. O n the other

hand, the patterns of the spectra of P-trifluoromediylporphyrins dramatically change as the

number of —CF groups increases (Figure 2-5). In Chapter I, section D . / . b , it was discussed that
3

UV-visible spectra of porphyrins are possibly affected by the electronic and steric effects of

substituents on the macrocycle. Takeuchi et al)-^ analyzed each effect on the H O M O s and the

L U M O s of a series of octa p-substituted /^^-tettalds(perfluoromediyl)-porphyrinato Zn(II)

(Zn(TPFPPX ), X = H , F, CI, Br, C H ) by semiempirical A M I calculations. In the theoretical

8 3

study, it was found that the H O M O - L U M O (71-71*) gap did not change appreciably if the

structure of the macrocycle was kept planar and only X (i.e. electronic effect) is varied.

(Zn(TPFPPF ) (12b) 8 was an exception, which showed a significandy larger gap. The rationale for

this is extremely strong electton-withdrawing effect of F according to Takeuchi et al\ 44) t

although the H O M O and L U M O vary from a Zn(II) porphyrin to another in the series. O n the
 101

Fi
g ur
e 2-5. UV-visible spectra of P-ttifluorormemyl-^j-o-tetaphenylporphyrm
(a) 46a, (b) 47a, and (c) 48a in CHC1. The narrow lines show ten times magnification
2 2

of the corresponding regions of the thick lines.

Fi
g ur
e 2-6. UV-visible spectra of P-tettabromo-^j-o-tetraphenylporphyrin (45a)
in CHC1. The narrow line shows ten times magnification of the corresponding
2 2

regions of the thick line.

F i
g u re 2-7. UV-visible spectra of P-memyl-^j-o-tetraphenylporphyrins,(a) 57a,
(b) 58a, and (c) 59a in CH C1
2 . The narrow lines show ten times magnification
2

of the corresponding regions of the thick lines.

 104

other hand, if the macrocycle distortion was the variable in each Zn(II) porphyrin, significant gap

contraction occurred along with macrocycle distortion. Thus, theoretically the pure electronic

effect causes littie change and the steric effect (macrocycle distortion) should red-shift absorption

maxima in UV-visible spectra. There was no implication that electton-withdrawing effects cause

red-shifts in UV-visible spectra. The theoretical study by Takeuchi et al. demonstrated that the

red-shifts observed in UV-visible spectra can be attributed mainly to the macrocycle distortion.

The estimated gap contraction by macrocycle distortion was a range of 0.1 — 0.2 eV, which

corresponds to 24 — 48 nm red-shifts of the lowest energy Q band. 44 1

X Ar x
X = H (4b)
= Br (8b)
= F (12b)
= CI (62)
= CH (63)
3

H T P P ( C F ) (47a)
2 3 3 and H T P P ( C F ) (48a)
2 3 4 show two broad Q bands (also a shoulder at

around 620 nm for 48a) and the red-shifts of the lowest energy Q band of 47a and 48a from the

that of F L T P P (2a) are 89 nm and 186 nm, respectively. These values are extremely large

compared to 24 - 48 nm obtained for Zn^TPFPPBrg) (8b) whose macrocycle is severely

distorted^Ol and thus it is unlikely that the large red-shifts of 47a and 48a were caused by

macrocycle distortion only. Furthermore, the red-shift of the lowest energy Q band of

H T P P B r (45a)
2 4 for that of H T P P (2a)
2 is 40 nm but the macrocycle of 45a is known to be

planar by X-ray crystal structure analysis.202 These results suggest that electton-withdrawing

effects of substituents should be involved in order to account for the red-shifts of 45a, 47a, and

48a.
 105

The second unusual feature in the UV-visible spectra of 47 a and 48a is the order of the

intensity of the Q bands; the Q band at the longer wavelength has a higher intensity which is

reversed in the spectra of 2a, 45a, H TPP(CF )

2 3 2 (
4 6a)
, and

p-methylporphyrins ( H T P P ( C H ) 2 3 2 (
5 7a)
, H TPP(CH ) (
5 8a)
, and H T P P ( C H ) (
2 5 9
3a)
)
. Only3 2 3 4

the spectrum of H T P P ( C N ) (34a,

2 4 x=4) 2 0 0
(Table 2-6) mimics those of H T P P ( C F ) (47a) 2 3 3 and

H TPP(CF )
2 3 4 (
4 8a)
. In the spectrum of 48a, the Soret band is split into two bands. The split of

the Soret band becomes more prominent in a presumably more electron-deficient porphyrin,

H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 (Figure 2-8). A similar spktting of the Soret band observed for 48a

and 52a can be observed for H T P P ( C N ) (34a, 2 4 x=4) (Table 2-6) as well. The difference between

P-tofluoromedaylporphyrins (47a, 48a and 52a) and 34a (x=4) is that the Q bands of 34a (x=4)

are resolved into four unlike the very broad ones observed for 47a, 48a, or 52a. The band widths

at the half intensity of the lowest energy Q bands are extremely broad; 94 and 122 nm for those

of 47a and 48a compared to 26 nm of H T P P (2a) (Figure 1-14) and 56 nm of H T P P B r (

24 5a)
. 2 4

The unusually broad Q bands are possibly caused by a hindered rotation of - C F groups that may 3

induce a change of the conformation of substituents (-CF and phenyl groups) and lead to a 3

fluctuation of electronic transitions. The details of the steric interaction and the conformation of

-CF 3 and phenyl groups are discussed in section B.4.(3) for the analysis of an X-ray crystal

structure of Zn(TPP(CF ) ) (48b).The unusual Q bands and the split of the Soret band are not
3 4

observed for meso- tettakis(trifluoromethyl)porphyrin (H (CF ) P) (16a 2 3 4 (n=l)) (Figure 1-8, p . l l ) .

39

Other noticeable results for p-perfluoroalkylporphyrins are the low extinction coefficients of the

Soret bands (1 - 3 x 10 M'cm" ) compared to the general range for porphyrins!^

5 1
a n c j a s irnilar

low extinction coefficient is seen in H (CF ) P (16a, 2 3 4 n=l). Presumably, rotation of - C F groups 3
 106

causes a fluctuation o f electronic transitions and leads to the broad absorption w i t h l o w

intensities.

300 400 500 600 700 800 900 1000

Wavelength (nm)

Fi
g ur
e 2-8. U V - v i s i b l e spectra o f 52a i n C H C 1 . T h e narrow line shows
2 2

ten times magnification o f the corresponding regions o f the thick line.

 107

The unusual spectral pattern, especially in terms of the pattern of the Q bands, of 47a, 4
8a

and 5
2a is similar to that of the UV-visible spectrum of P-tetrahyckoporphyrin

(bacteriochlorin) (64) (Figure 2-9). Thus, porphyrin 47a, 48a, and 5

2a may have a similar

electronic structure to that of bacteriochlorin (64), although the Q bands of H T P P ( C F ) (

2 4 7a
3)
, 3

H T P P ( C F ) (48a) and H T P P ( C F ) ( C F C F ) (52a) are not as intense and sharp as those of 64.
2 3 4 2 3 3 2 3

As shown in Scheme 2-9(a), bacterichlorin (64) is only allowed to take one 187T-electron

conjugated pathway (shown by the dotted line in the structure). The unique spectral pattern of

64, for example, compared to that of H T P P (2a)(Figure 1-14, p.39), is due to the distorted
2

electronic pathway.203 The distorted electronic pathway of 6

4 also results in the H O M O -

L U M O gap contraction and thus leads to the red-shift of the low energy Q band.!42,204,205 \

rationale for the possibly similar electronic pathway of P-trifluoromethylporphyrins to that of 6

4

is that the reduced electron density of the pyrrolic P-C-C bonds where —CF groups reside may
3

be disadvantageous for the conjugated 1871-electron path.

As discussed in Chapter I, section DJ.c, there are two possible tautomers for H T P P (2a)
2

in terms of the 187X-electron pathway or the location of N - H protons (see Figure 1-25, p.59) and

the two tautomers are indistinguishable at room temperature, leading to an averaged

derealization of the two electronic pathways. Unlike the case in 2a, the electronic pathways in

P-trifluoromethylporphyrins 47a, 48a, and 5

2a may be distorted as in bacteriochlorin (64) due to

the strong electron-withdrawing substituents on the P-position of the pyrroles in the antipodal

positions. These may result in the structure shown in Scheme 2-9(b). In order to assess the

electronic pathway of trifluoromethylated porphyrins, H N M R experiments to determine the

a

location of N H protons were attempted through which the electronic pathway could be
 R = H: H TPP(CF )
2 3 3 (47a)
R = C F : H TPP(CF )
3 2 3 4 (48a)
R = C F C F : H T P P ( C F ) ( C F C F ) (52a)
2 3 2 3 3 2 3

Scheme 2-9. (a) 187T-electron pathway of bacteriochlorin (64) and

(b) the possible electronic pathway of P-ttifluoromethylporphyrins.
 109

determined. The results of the N M R experiments are shown later (p. 116).

In summary, red-shifts in the UV-visible spectra of the P-tafluoromethylporphyrins are

possibly caused by macrocycle distortion as well as electronic effects. As shown in Table 2-6, as

the number of the perfluoroalkyl moieties increases (2a —

» 46a —
» 47a —
» 48a —
> 52a), the

absorption maxima in the spectra progressively shift to longer wavelengths. The observed red-

shifts were unusually large for the effect of macrocycle distortion alone. The strong electron-

withdrawing effect of —CF groups on the pyrrolic P-positions of antipodal pyrroles may be
3

affecting the electronic structure that is probably similar to that of bacteriochlorin and results in

the unusual UV-visible spectra of the P-trifluoromethylporphyrins.

(2) Absorbance vs. concentration of 48a

According to Ono etal^Z a s discussed in Chapter I, section D.i.b., it seems that electron-

deficient porphyrins have some tendency to aggregate. Since p-trifluoromethylporphyrins are

extremely electron-deficient, aggregation of P-trifluoromethylporphyrins might occur. There are

also reports that sphtting of the Soret band is occasionally accompanied by porphyrin

dimerization.206,207 As shown in Figure 2-5, the Soret bands of H T P P ( C F ) (48a) 2 3 4 and

H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 split. This may be an indication of aggregation of porphyrins. In

order to examine aggregation of P-trifluoromethylporphyrins, the behavior of Ff TPP(CF ) 2 3 4 (48a)

and H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 in solution was investigated by UV-visible spectroscopy.

Aggregation of porphyrins is often detected in the concentration range, 10" - 10" M.^69 As this 4 7

concentration range is suitable for UV-visible spectroscopy, the spectral changes with

concentration for 48a and 52a in C H C 1 and benzene were investigated.

2 2
 110

Figure 2-10 shows the UV-visible spectral change of 48a in CH C1 and absorbance vs.
2 2

concentration plot over the concentration range 5.90xl0~ to 2.95xl0~ M.

7 4
Perfect linear

correlation between absorbance and concentration at five different wavelengths was obtained

with coefficients of correlation close to 1.208 j should be noted that usually absorbance 1.5 is
t

the upper limit for analysis of Beer's law. The plot of the data at 620 nm, however, proves the

linear relationship of the concentration and the absorbance. Figure 2-11 shows that a similar

result obtained for 52a in CH C1 .

2 2 The same experiments using 48a in benzene in the similar

concentration range also showed the linear correlation between absorbance and

concentration (data not shown). These results show that the structures of 48a and 52a are

retained in solution in a range of concentrations (5.90 x 10~ - 2.95 x 10~ M). Since non-linear 7 4

spectral changes were not detected in this concentration range, it was presumed that

P-trifluoromethylporphyrins (48a and 52a) are monomelic in solution in the range of the

concentration for the UV-visible spectroscopy.

b. UV-visible spectra of metalloporphyrins

Figure 2-12 shows the UV-visible spectra of Zn(TPP(CF ) ) (48b) 3 4 and

C o ( T P P ( C F ) ) (48e)
3 4 in CH C1 . For comparison, the spectrum Z n ( T P P ) (2b)
2 2 is also shown with

that of 48b. Although the absorption bands are broad, the Soret bands do not split. As shown in

Table 2-7, the absorption maxima of Zn(TPP(CF ) ) (48b) 3 4 were red-shifted and the extinction

coefficients were decreased compared to those of Z n ( T P P ) (2b). O n the other hand, the

positions of absorption maxima and extinction coefficients of Z n ( T P P ( C H ) ) (59b) 3 4 are similar

to those of Z n ( T P P ) (2a). Thus, electronic and structural deviations of the macrocycle in 59b

may be very small from those of Z n ( T P P ) (2a). The red-shift of the Q band is 114 nm from that

of 2b to 48b. As described in the discussion of the UV-visible spectra of

 Ill

(a)

Concentration X 10 (M) 4

Figure 2-10. (a) UV-visible spectral change of H T P P ( C F ) (48a) over the concentration
2 3 4

range from 5.90 X 10" to 2.95 x 10" M in C H C 1 at room temperature.

7 4
2 2

(b) Absorbance vs. concentration plot at 444 (O), 463 (•), 580 (•) , 620 (•) and 832 nm (A).
 112

Concentration X 10 (M)4

Figure 2-11. (a) UV-visible spectral change of H T P P ( C F ) 3 ( C F C F ) (52a) over the

2 3 2 3

concentration range from 9.87 X 10" to 2.47 x 10" M in C H C 1 at room temperature.

7 4
2 2

(b) Absorbance vs. concentration plot at 444 (O), 468 (•), 586 (•) , 628 (•) and 844 nm (A).
 113

Figure 2-12. UV-visible spectra (thick lines) of Zn(TPP(CF ) ) (48b) and

3 4

CoCrPP(CF ) ) (48e) in CH C1 . The narrow line is Zn(TPP) (2b).

3 4 2 2
 114

P-trifluoromethyl porphyrin free-bases, red-shifts caused by a large macrocycle distortion is at

best 24 — 48 nm according to calculations by Takeuchi et al}^ Therefore, the large red-shift of

the Q band in 48b must be attributed to both the steric and electronic effects.

Tabl
e 2-1. UV-visible absorption maxima of metalloporphyrins.
Porphyrin A,max (nm)(log s)
Zn(TPP) (2b) 419 (5.83), 548 (4.36), 582 (3.41)
Zn(TPP(CF ) ) (48b) 3 4 442 (5.37), 662 (4.31)
Zn(TPP(CH ) ) (62b) 3 4 420 (5.63), 551 (4.26), 584sh(3.66)
Co(TPP(CF ) ) (48e) 3 4 440 (5.06), 636 (4.32)
Fe(TPPBr )Cl (45e)
4 433 (5.02), 520 (4.11), 591 (3.81), 700 (3.56)
Fe(TPP(CF ) )Cl (48f)3 4 452 (4.76), 618 (4.12)
Fe(TPP(CF ) (CF CF ))Cl (52c)
3 3 2 3 459 (4.62), 624 (4.00)
(FeTPP(CF ) ) Q (61) 3 4 2 435 (1.00)* 700 (0.27)*
( )* : relative intensity

A rationale for explaining why the Soret bands of Zn(TPP(CF ) ) (48b)

3 4 and

Co(TPP(CF ) ) (48e)
3 4 do not split is that the postulated distorted electronic pathway (Scheme 2-9)

may be disturbed by metallation. However, the macrocycles seem be forced to take an unusual

electronic structure even in the presence of a central metal. For instance the Soret band of 48b is

not completely symmetric, indicating an overlap of two bands, and the pattern of the Q bands

are significandy different from that of Zn(TPP) (2b).

Figure 2-13 shows the UV-visible spectra of hemins (Fe(III)Cl complex)

Fe(TPPBr )Cl
4 (
4 5e)
, Fe(TPP(CF ) )Cl (
4 8f
), and FeCTPP(CF ) (CF CF ))Cl (
3 4 5 2c)
. The absorption 3 3 2 3

maxima and extinction coefficients are also listed in Table 2-7. The Soret bands of 48f and 52c

red-shift from that of 45e and the intensities of the absorption bands progressively decrease as

the number of perfluoroalkyl moieties increases. The p,-oxodimer Fe(III) complex (61) showed

very broad UV-visible bands and a low ratio of intensity of the Soret to the Q band (Soret/Q
 45e 48f 52c

12

300 400 500 600 700 800 900 1000

Wavelength (nm)

Fi
g ur
e 2-13. UV-visible spectra of [FeTPP(CF ) ]Cl (
438f
)
(—)
,
4

[FeTPP(CF )3(CF CF )]Cl (

3 2 5 2
3c)
(
— , [FeTPPBr ]Cl (
) 4 5e)
( —) in C H C 1 .
4 2 2
 116

band intensities = 3.7) compared to Soret/Q band intensities = 6.6 of the u,-oxo dimer Fe(III)

complex of 45 ( ( F e T P P B r ) 0 ) .
4 2
192

In summary, the UV-visible spectra of metalloporphyrins of 48 and 52 show red-shifted

and very broad absorption bands with decreased extinction coefficients compared to those of

metalloporphyrins of H T P P (2a),2 H TPPBr (

2 4 5a
4)
, and H T P P ( C H ) (
2 539a)
. This is a pattern
4

similar to that observed for the corresponding free-base species. The presence of the electron-

withdrawing and steric effect of trifluoromethyl groups (see Chapter II, section B.4.b.(3) for the

discussion of the sizes of —CF and — C H groups) may lead to the characteritic UV-visible
3 3

absorption bands of these novel P-tiifluoromethylmetaUoporphyrins.

2. NMR spectroscopy

As discussed in Chapter I, section D . i . c , electronic effects of a P-substituent on the

porphyrin macrocycle can affect the 1871-electron pathway, or the location of N H protons of the

porphyrin macrocycle, while very unusual UV-visible spectra of P-trifluoromethylporphyrins

were obtained. EspeciaUy, the UV-visible spectra of H T P P ( C F ) (

4 7a)
, H TPP(CF ) (
2 3 4 8
3a)
, and 2 3 4

H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 showed a similarity to that of bacteriochlorin (64), indicating these

P-trifluoromethylporphyrins have a similar electronic structure to that of 64. The major purpose

of this section is to determine the electronic structure of p-trifluoromethylporphyrins by

N M R spectroscopy. The analysis of the positions of N - H protons was achieved by inference

through ' H C O S Y or H homonuclear decoupling experiments. The second part of this section
l

describes an unusual chemical shift of P-pyrrolic protons of p-tetrakis(trifluoromethyl)-meso-

tetraphenylporphyrin (
4 8a)
.
 117

a. Determination of electronic pathway of B-trifluoromethylporphyrins.

As shown in Figure 1-25, the N - H tautomerism accompanies the tautomerism of the 187T-

electron pathways of the macrocycle. Tautomerism is generally fast on the N M R time scale at

room temperature and we cannot assign the N - H protons on specific pyrroles. 166
However,

when the temperature is lowered the tautomerism is slowed. For example, the H N M R showed :

two resolved lines for the two kinds of pyrrolic P-protons ( H A

and H B
in Figure 1-25) of

H T P P (2a)
2 below 220 K.174 Electronic effects of substituents on the macrocycle are also

known to affect the tautomerism of a macrocycle (see Chapter I, section D.J?.C). According to a

low temperature N M R study, 1

187t-electton pathway of the porphyrin tends to avoid a

pyrrolic Cp-Cp bond where an electron-withdrawing substituent resides because of the reduced

electron density. It may be worth mentioning the *H N M R of H T P P B r (45a) 2 4 reported by

Crossley etal.^^ in which a long-range coupling between N - H and pyrrolic p - H was observed.

Figure 2-14 shows the ' H N M R spectra of 45a obtained by the author. The doublet of pyrrolic

P - H with a coupling constant of 1.4 H z is due to the long-range coupling between N - H and

pyrrolic P - H which is decoupled by irradiation at N - H (the doublet of P - H can be observed by a

200MHz spectrophotometer as well).

Long range H-H couplings (i.e. over four or more bonds) are sometimes observed in a

planar zig-zag orientation (the structure is shown below) and an approximate representation of

theoretical calculations for a / i .

4
H H 2 coupling in unstrained systems is given by (2.1):

^C^ o % .
1 H 2 = cos (j) + cos (|) -0.7
2
1
2
2 (2.1)
H C hr

where (j^ and <)> are the H - C ' - C ^ - C

2
3
and C - C - C - H
1 2 3 2
dihedral angles in the coupling
 1 ; 1 1 j 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 j 1 1 1 r

8.6 8.4 8.2 8.0 7.8

Chemical shift (ppm)

(b) I

Chemical shift (ppm)

Fi
g ur
e 2-14. 4
00MHz *H nmr spectra of H TPPBr (45a) 2 4 in C D C 1 at room temperature,
3

(a) Normal spectrum.J(NH-pH)=1.4 Hz.

4
(b) Decoupled at -NH (-2.88ppm).
 119

cx
aromatics cyclohexanes
meta equatorial-equatorial
4
/=2-3Hz 4
/=l-2Hz

pathways.209 The examples of such long-range couplings are shown b e l o w . ^ The commonest 2

example of a long-range coupling is the meta J coupling of 2 — 3 H z in aromatics. Long-range

4

couplings are also observed in saturated systems such as the equatorial-equatorial coupling (1 —

2 Hz) in cyclohexanes and even a / coupling can be observed for H and H in quinoline.
5 4 8

Pyrroles are planar aromatic systems and have such zig-zag orientations between N - H and

P-H and thus observing a J coupling of ~1 H z between N - H and p - H coupling is reasonable. In

4

porphyrin 45a the N - H - P - H coupling can be observed at room temperature (see ' H N M R

spectrum of H T P P (2a)
2 at room temperature (Figure 1-23) for comparison). Thus, the N - H

localization tells us that the macrocycle has a specific 187t-electron pathway as shown in

Figure 2-14.

Using H T P P ( C F )
2 3 3 (
4 7a)
, which resulted in a bacteriochlorin-type UV-visible spectrum,

determination of the positions of N - H protons was attempted. Figure 2-15 shows the 400 M H z

l
H N M R spectrum of 47a. The reason porphyrin 47a was used was that H (see the structure of
5

47a in Figure 2-15) could be a good probe to determine the electronic pathway for the analysis

of correlation between pyrrolic P - H and N - H protons. The spectrum shows the N - H protons

(two broad singlets at -1.73 and -1.86 ppm), meta+para-phenyl-H (7.66 - 7.81 ppm), ortho-

phenyl-H (8.11 - 8.24 ppm), and pyrrolic P - H (8.30 - 8.77 ppm). It is easy to assign H 5
because

it appeared as a singlet and other pyrrolic P-Hs (H , H , H , and H )

1 2 3 4
appeared
 CHCL
(a)

H 5
Ph H1

47a

U
i r i r "i r
_
i i r
10 9 6 5 4 3 2 1 0 -1

Chemical shift (ppm)

(b)
»./>-phenyl-H(12H)

I I I I 1 1 I 1 » — i 1 1
9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 -1.7 -1.9

Chemical shift (ppm)

Fi
g ur
e 2-15. 400 M H z H N M R spectra of H T P P ( C F ) (47a) in C D C 1
J
2 3 3 3

at room temperature.(a) Full spectrum and (b) expansion of the peaks.

Peaks labeled with * are impurities.
 121

Fi
g ur
e 2-16. 400 M H z C O S Y spectra of H T P P ( C F ) (
2 3 34 7a)
. (a) Full spectrum
and (b) expansion of one of the circled areas.
 122

as doublets due to coupling to adjacent protons; H - H 2

and H - H * . Assignment of each of H ,
3

H , H and H was not attempted, since it was unnecessary for determination of the electronic
2 3 4

pathway. Unlike the case of H T P P B r 2 4 (

4 5a)
, the 400 M H z H N M R of H T P P ( C F ) (47a) did
]
2 3 3

not show the fine splitting of pyrrolic (5-H signals. However, the coupling connectivity between

pyrrolic P - H and the N - H protons was observed by a C O S Y experiment at room temperature, as

indicated by the dotted circles in Figure 2-16(a). Expansion of the correlation (Figure 2-16(b))

clearly showed that the N - H protons are not coupled to H but to H , H , H , and H . By the
5 2 3 4

experiment it can be concluded that locations of the N - H protons are assigned on the pyrroles

not substituted by —CF groups and thus at room temperature the porphyrin preferably takes the
3

electronic structure shown in the box in Figure 2-17. During the course of the N M R

Ph C F 3

CF
iW
3

V-NH
Ph- -Ph

F C-
3

H Ph H Ph

Fi
g ur
e 2-17. 187t-electeon pathway of H T P P ( C F ) (
4 7a
2)
. 3 3

experiments, it was also discovered that N - H protons of H T P P ( C F ) (47a) 2 3 3 can exchange easily

with residual water. The observation is shown in Figure 2-18(a) and (b). In the presence of trace

water (Figure 2-18(a)), the signals from water and N - H protons are broad. In the absence of

water (Figure 2-18(b)), on the other hand, the spectra showed two N - H proton signals clearly. In

addition to this observation, intensities of H , H , H , and H signals dropped significantly and

1 2 3 4

peak widths were obviously greater compared to those observed in Figure 2-18(a). In contrast,

such significant changes were not observed for H 5

and o-phenyl-H signals. The
 123

CHCL

(a)

H 5

8.60 8 .40 8 .20 8.00 (PP ) m

H 0
2
N H

"""I' r i "i—i—i—i—[—i—[—rI—[—i—i—r~r
-
i I i i ii
5 4 3 2 1
Chemical shift (ppm)

(b) o-phenyl-H

H 5

H ^ H ^ H 4

^
r

30 8.60 8.40 8.20 8.00 (PP ) m

NH

inwtHimiii*iiimin*i ».i>mw>i< s*— niiirtiiMil II>II|IHI#IH iimUwi>i'i UNI i'mfim n Df'tlt«

I ' I
11 1 1
n^ ' i ' ' i
-1- 1 1

8 7 4 3 2 1 0 -1 -2 -3

Chemical shift (ppm)

Fi
g ur
e 2-18. 200 MHz H NMR spectra of HTPP(CF) (47a)
!
2 33 (a) in the presence of
and (b) in the absence of residual water in CDC1 . Inner traces are expansion of the 3

region of pyrrolic P - H and or^o-phenyl-H. Designation for pyrrolic P-Hs was given
in Figure 2-15.
 124

change from Figure 2-18 (a) to (b) evidently confirms the electronic pathway of

H T P P ( C F ) (47a)
2 3 3 as shown in Figure 2-17.

The coupling connectivity between the N-H and the P-H protons in

P-tettakis(trifluoromemyl)porphyrin H T P P ( C F ) (48a)
2 3 4 seems not as strong as that of 47a.

Unlike the P-H signal of H T P P B r (45a)(doublet, see Figure 2-14), the P-H signal of 48a was a
2 4

sharp singlet and the coupling connectivity could not be observed by a C O S Y experiment either.

However, there was a slight increase of the absolute intensity of P-H upon irradiation at

N-H (-1.42 ppm) and the intensity of o-phenyl-H and w+/)-phenyl-H signals was unchanged.

Although a clear evidence for the connectivity between N-H and P-H protons for 48a was not

obtained, this is also a phenomenon expected from the porphyrin having an electronic structure

as shown in Figure 2-17 deft). A coupling through bonds is transmitted via the bonding

electrons.209 Accordingly, it should be harder to transmit the coupling if the density of bonding

electrons is lowered. Although the orientation of the N-H and P-H in the pyrroles may satisfy

the criterion for a long-range coupling (planar zig-zag orientation), a possible reason for not

observing a spurting of the P-H signals due to long-range couplings between the N-Hr and P-Hr

may be the lower electron density of the macrocycle induced by the strong electton-withdrawing

effect of the —CF groups.3

Analysis of the electronic pathway of P-ttimethylporphyrin H T P P ( C H ) (58a) 2 3 3 was also

attempted. However, any information that suggests the porphyrin takes a specific electronic

pathway could not be obtained. As shown in Figure 2-19, the N-H signals are quite broad even

in the absence of water, indicating N - H tautomerization at room temperature.

 125

10 9 8 7 6 5 4 3 2 1 0 -1 -2 -3
Chemical shift (ppm)

0)
•CH O ~ 3 P C
3
(6H)
(3H)
«?+/)-phenyl-H(12H)
• = H',H ,H ,H
2 3 4

o-phenyl-H(8H)

T—r-ft 1 1 i 1 . 1 1 . 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 .
8.6 8.4 8.2 8.0 7.8 7.6 3.0 2.8 2.6 2.4 2.2 2.0
Chemical shift (ppm)

Fi
g ur
e 2-19. 400 M H z H N M R spectra of H T P P ( C H ) (58a)
l
2 3 3 in C D C 1 3

at room temperature, (a) Full spectrum, (b) Expansion of the selected peaks.
Peaks labeled with * are impurities.
 126

These observations for P-trifluoromethyl and P-methylporphyrins by NMR

spectroscopy suggested that in order to observe the coupling connectivity between the N - H and

the P~H, a porphyrin may have to satisfy at least the following conditions: (1) the porphyrin has

substituents on the antipodal pyrroles and (2) the substituents are moderately electron-

withdrawing. The ' H N M R experiments showed that at room temperature the 187T—electronic

pathways for P-tris- and P-tettaltis(teifluoromethyl)porphyrins (47a and 48a) are fixed so that

they avoid the paths where —CF groups reside because of the reduced electron density. This
3

result is similar to those obtained for p-mono-substituted wwo-tetraphenylporphyrins ^ 17

(Chapter I, section D.3.) but it has to be emphasized that one of the N - H tautomers can be

locked at room temperature presumably due to the strong electron-withdrawing effects of —CF 3

groups. O n the other hand, a

H N M R spectra of P-tjimethylporphyrin H T P P ( C H ) 2 3 3 (58a)

suggested that tautomerization of the N - H protons or the electronic pathways occur as is the

case of H T P P (2a).
2 The results obtained by the N M R studies for P-trifluoromethyl- and

p-metliyl-porphyrins agree with the prediction made by the UV-visible spectra of these

porphyrins in terms of the electronic structures.

b. Unusual 'H NMR chemical shiftfor pyrrolic ^-protons ofH TPP(CF ) 2 3 4 (48a)

The chemical shift for the pyrrolic p - H of H T P P ( C F ) (48a) 2 3 4 appears at fairly high field

compared to those of other wwo-tetraphenylporphyrin derivatives such as H T P P B r (45a) 2 4 or

H TPP(CH ) (
2 5 9a)
. This part of the N M R section is a discussion of the possible origin of this
3 4

unique chemical shift for the pyrrolic P-protons of H T P P ( C F ) (

4 8a)
. Figure 2-20 shows the
2 3 4

200 M H z 'HNMR of H T P P (2a)

2 and P-tetrasubstituted-^j-o-tetraphenylporphyrins

H TPPBr (
2 4 5a)
, H TPP(CF ) (
4 4 8a)
, and H T P P ( C H ) (59a)
2 3 4 2 3 4 in Q D . The porphyrin 48a is the
6
 B-H

N H chem. shift
(ppm)

(a) m,p-phenyl-H
o-phenyl-H
-2.13

9 . 0 8 . 8 8 . 8 8 . 4 8 . 2 8 . 0 7 . 8 7.6 7.4 7.2

m,p-ph.eny\-H

(b) B-H o-phenyl-H

-2.69

9 . 0 8 . 8 8 . 6 8 . 4 8 . 2 8 . 0 7 . 8 7 . 6 7 . 4 7 . 2

p-H /»,/>-phenyl-H

(c) <?-phenyl-H
-1.42
' ,1
Mir**-*?

J.O 8 . 8 8 . 6 8 . 4 8 . 2 8 . 0 7 . 8 7 . 6 7 . 4 7 . 2

«,/>-phenyl-H

(d)
o-phenyl-H
-2.72

9 . 0 8 . 8 8 . 6 8 . 4 8 . 2 8 . 0 7 . 8 7 . 6 7 . 4 7 . 2

C h e m i c a l Shift (ppm)

Fi
g ur
e 2-20.200 M H z H N M R spectra o f (a) H T P P (2a),
l
2 (b) H T P P B r (
2 445a)
,
(c) H T P P ( C F ) (48a)
2 3 4 and (d) H T P P ( C H )
2 3 4 (59a) i n C D a t r o o m temperature
6 6

* is 1 3
C satellite o f benzene.
 128

most soluble in benzene but unfortunately is sparingly soluble in CHC1 in neutral conditions.
3

Accordingly, the comparison of the N M R spectra was performed in C D . (Porphyrin 48a is also
6 6

very soluble in T F A and the N M R spectra of related porphyrins in T F A - d will be shown later in

this section.) The concentrations of porphyrin 45a, H T P P ( C F ) (

2 4 8a)
, and Ff TPP(CH )
3 4 2 3 4 (59a)

were set to 0.0025 - 0.003 M (~ 1 mg porphyrin/0.5 m L QDg). The concentration of

H T P P (2a)
2 was 0.0065 M . Porphyrin 48a is very different from other porphyrins in terms of the

chemical shift of pyrrolic (3-protons and N - H protons. A l l the porphyrins (2a, 45a, 48a, and 59a)

have phenyl groups on the wwo-positions of the macrocycle and the chemical shifts for phenyl

protons appear at similar chemical shifts. This indicates that the environment of phenyl

substituents is independent of the macrocycle structures, although there might be some

interactions between P-substituents and ort/w-phenyl-Hs. Two possibilities were considered for

the unusual chemical shift of pyrrolic P-proton signal of 48a. The first possibility is a

deterioration of ring current due to a macrocycle distortion and strong electron-witiidrawing

effect. The P-pyrrolic protons are deshielded and the N H protons are shielded due to the ring

current effect of the macrocycle (Chapter I, section DJ.a. for the ring current and chemical

shifts). The —CF group is a strongly election-withdrawing and bulky substituent. Accordingly,
3

the macrocycle in 48a is expected be electron-deficient and distorted (see Chapter II,

section B.4.b.(3) for steric interaction between substituents and a macrocycle distortion of

Zn(TPP(CF ) ) (
4 8a
3)
)
. Consequendy, the smooth ring current is possibly hampered by the
4

electronic and the steric effects of the - C F groups and deshielding and shielding effects will be
3

weakened. Appearances of the pyrrolic P-proton signal at the higher field (ca. 0.9 ppm shift from

that of H T P P (2a)
2 and of the N H proton signal at the lower field (ca. 0.6 ppm shift from that

of 2a) are explained by this hypothesis.

 129

The second possibility is an aggregation. As shown by O n o et alX^^ (Chapter I,

section D.i.b.), P-pyrrolic protons shift to the higher field when the porphyrins aggregate.

Aggregation of porphyrin 48a and H T P P ( C F ) 3 ( C F C F ) (52a)

2 3 2 3 has already been investigated

using UV-visible spectroscopy for a concentration range of K T - 1 ( T M and the monomer 7 4

form of the porphyrins was suggested. Since the concentration of 48a for the N M R spectrum

shown in Figure 2-20 was much higher than those examined in the UV-visible spectroscopy, the

possibility of aggregation was investigated. A t 0.00045 M , 0.001 M , and 0.002 M (0.9 mg/0.5 m L

was the maximum concentration) the chemical shift of p-pyrrolic protons of 48a appeared

always at 8.00 ppm. It should be noted that 0.00045 M is nearly equal to the maximum of the

concentration range investigated by the UV-visible spectroscopy. This means the structure of

porphyrin 48a is unchanged and presumably exists as monomers in the concentration of I O — -7

2 x 10 M in benzene. Thus, the large highfield chemical shift of pyrrolic P-protons and
3

lowfield chemical shift of N H protons of H T P P ( C F ) (48a)

2 3 4 are probably due to a macrocycle

distortion. In fact, a large downfield shift of N H (that appears at -0.5 ppm) of P-octabromo-

^jo-tetrakis(perfluorophenyl)porphyrin (I^TPFPPBrg)(8a)(Figure 1-8, p.11) from that

(-2.76 ppm) of HTPP(2a), was explained by a severe macrocycle distortion of

2 8a.^6

The unusual chemical shift of pyrrolic P-protons of 48a was also observed in deuterated

ttifluoroacetic acid (TFA-d). Comparison of the ' H N M R spectrum of 48a with H T P P B r 2 4 (45a)

and H T P P ( C H ) (59a)
2 3 4 is shown in Figure 2-21.* Figure 2-21 (a) shows the spectrum of 48a in

T F A - d . The assignment of the signals was done by comparing the peak integrations. The pyrrolic

UV-visible spectra o f diacids o f 48a and 59a are shown i n appendix B (P.233).
 130

B-H(4H)
/»,/)-phenyl-H(12H)

1 • i—i • | i—i I—• | . I I i 1 . 1 1 • 1 1 1 1 . |—i 1 1 1 1 1 ,,,1 ,—r-

9.40 9.20 9.00 8.80 8.60 8.40 8.20 8.00

Chemical shift (ppm)

Fi
g ue 2-21. 400 M H z *H N M R spectra of diacid of (a) H T P P ( C F ) (
r 4 8a)
, 2 3 4

(b) H T P P B r (45a)
2 4 and (c) H T P P ( C H ) (59a)
2 3 4 in T F A - d at room temperature.
 131

P - H for 48a appeared at 8.28 ppm as a sharp singlet and the chemical shift was about 0.5 ppm

higher than those for pyrrolic P - H of 45a (Figure 2-21 (b)) and 59a (Figure 2-21 (c)), indicating

that there are macrocycle distortions and electron-withdrawing effects of - C F groups in 48a. 3 An

interesting observation in the N M R spectra of these porphyrins in T F A - d is that porphyrin 45a

and 59a showed splitting of the o-phenyl-H signal into two peaks with equal area but 48a

showed only one peak for c-phenyl-H. It is known that protonation of the macrocycle of

^jo-tetraarylporphyrins causes severe macrocycle distortion into a saddle shape and the

distortion accompanies rotation of the meso-atyl groups along the C - C axis between the

porphyrin macrocycle and the aryl groups.^ -0,211 Modes of distortion of the macrocycle upon
1

protonation are shown in Figure 2-22. The structures in the figure were created by

HyperChem.188 T nm e diacid form of D 4 h porphyrins such as Ff TPP (2a),

2 all o-phenyl-Hs are

equivalent (Figure 2-22(a)), which has been observed by X-ray crystal crystallography^l 0,211 anc j

!
H N M R in TFA-d.212 Since the pyrrole rings are alternately tilted up and down to the average

plane of the macrocycle, in the case of D 2 h porphyrins such as H T P P B r (45a)

2 4 or

H TPP(CH )
2 3 4 (
5 9a)
, a distorted porphyrin macrocycle should have two different faces regarding

the average plane of the macrocycle (Figure 2-22 (b)) and it is reasonable for D 2 h porphyrins to

have two kinds of non-equivalent o-phenyl-Hs and to show two peaks in the N M R spectra.

However, this analysis does not fit to the N M R spectrum of H T P P ( C F ) (48a) 2 3 4 in T F A - d which

shows only one broad singlet for o-phenyl-Hs. A rationale for this observation may be rotation

of - C F 3 groups. One piece of information regarding rotation of - C F 3 groups is that the

1 9
F N M R spectrum of H T P P ( C F ) (48a)
2 3 4 shows a sharp singlet at room temperature. The steric

interaction between the meso-phenyl groups and - C F groups on the pyrrolic P-positions was
3

found to be significant (see Chapter II, section B.4.b.(3)). Thus, rotation of - C F 3 possibly
 132

Fi
g ur
e 2-22. Structures of (a) [ H T P P ] and (b) [ H T P P ( C H ) ] .
4
2+
2 3 4
2+

Molecular structures were created by HyperChem geometry

optimization ( M M + ) . 189
 133

induces rotation of meso-phenyl groups along the C - C axis between the macrocycle and the

phenyl groups. As a result of the continuous conformation change, o-phenyl-Hs may lose non-

equivalency and show one peak in the N M R spectrum in spite of the mode of distortion in the

D a porphyrin upon protonation.

Unlike the cases of the free-base and diacid form of H T P P ( C F ) 2 3 4 (

4 8a)
, the N M R

spectrum of Zn(TPP(CF ) ) (48b) 3 4 in CDC1 at room temperature showed a pyrrolic p-H signal
3

shifted the most downfield (8.43 ppm) compared to other two chemical shifts of o-phenyl-H at

8.07 ppm and ^ - p h e n y l - H at 7.76 ppm (Table 2-8). The electron-deficiency of 48a may be

relaxed by metallation with Zn(II) and the ring current may be increased. O n the other hand,

other Zn(II) porphyrins in the table did not show significant change in chemical shift of the

pyrrolic P-H from those of corresponding free-base porphyrins.

Tabl
e 2-8. Chemical shift values of zinc P-tetrasubstituted /^o-tettaphenylporphyrins
' H (ppm)
porphyrin solvent
P-H o-phenyl-H #?,/>-phenyl-H
Zn(TPP(CF ) ) 3 4 (48b) 8.43 (s, 4H) 8.07 (m, 8H) 7.70 (m, 12H) CDC1 3

H TPP(CF )
2 3 4 (48a) 8.00 (s, 4H) 8.11 (m, 8H) 7.45 (m, 12H) QD 6

Zn(TPP(CH ) ) 3 4 (59b) 8.65 (s, 4H) 8.06 (m, 8H) 7.75 (m, 12H) CD C1 2 2

H TPP(CH )
2 3 4 (59a) 8.44 (s, 4H) 8.07 (m, 8H) 7.71 (m, 12H) CDC1 3

Zn(TPPBr ) (45b)4
8.61 (s, 4H) 8.02 (m, 8H) 7.80 (m, 12H) DMSO-d 6

H TPPBr
2 (45a)4 8.68 (d, 4H) 8.18 (m, 8H) 7.78 (m, 12H) CDC1 3

Zn(TPP) (2b) 8.90 (s, 4H) 8.08 (m, 8H) 7.73 (m, 12H) CDC1 3

H TPP
2 (2a) 8.86 (s, 4H) 8.22 (m, 8H) 7.75 (m, 12H) CDC1 3

In summary, H N M R experiments using H T P P ( C F ) (47a)

]
2 3 3 and H T P P ( C F )
2 3 4 (48a)

showed that the positions of the N - H protons were locked at room temperature due to —CF 3

groups on the antipodal pyrroles. The positions of the N-H protons in the

P-Oifluoromethylporphyrins indicate that the 187t-electronic pathway of the macrocycle avoids

positions where —CF groups reside. Positions of the N - H protons in P-trimethylporphyrin

3

H T P P ( C H ) (58a)
2 3 3 were not resolved by the N M R experiment at room temperature,
 134

presumably due to exchange of the two possible N - H tautomers. Thus, for a locked N - H

tautomer or 187t-electton pathway, strong electxon-withdrawing effects by substituents will be

required. The analysis by the N M R experiments concerning the electronic structure of the

macrocycle agrees with the prediction deduced from the UV-visible spectroscopic data that

P-trifluoromethylporphyrins may have a fixed 187t-electron pathway similar to that of

bacteriochlorin.

The unusual chemical shift of the pyrrolic P-proton signal is characteristic of

H T P P ( C F ) (48a) and is possibly caused by the electton-withdrawing and steric effects of —CF
2 3 4 3

groups.

3. Redox potentials

As discussed in Chapter I section D . Z b , electron-withdrawing substituents positively shift

the reduction and the oxidation potentials of the porphyrin macrocycle and thus comparison of

the redox potentials enables us to estimate the electron-deficiency of porphyrins. So far, we have

seen the dramatically different characteristics of P-t^fluoromethyl-^Jo-tettaphenylporphyrins

from those of wwo-tettaphenylporphyrin, p-tettabromo-^ro-tettaphenylporphyrin, and

P-methyl-^j-o-tetraphenylporphyrins in their UV-visible and N M R spectra. The effects of the

strongly electton-withdrawing - C F groups were analyzed qualitatively by those methods. This

3

section describes direct quantitative analysis and comparison of electronic properties of

P-trifluoromethylporphyrins with those of other related porphyrin systems such as

Wcvo-tetraphenylporphyrn or p-methylporphyrins based on their results obtained from cyclic

voltammetry. The purpose of this section is to estimate electron-deficiency of

P-trifluoromethylporphyrins and to show some supporting evidence that agrees with those
 135

analyses in the previous sections regarding the 187t-electron pathway of the porphyrins. This

section is separated into three parts. The first part describes comparison of the ring redox

potentials of free-base P-tofluoromemylporphyrins with those of other

^j"o-tetraphenylporphyrin derivatives and how the redox potentials changes as the number of —

CF 3 group increases. The second part focuses on comparison of the redox potentials of

P-tettasubstimted-^j'O-tettaphenylporphyrinato Zn(II) complexes in order to investigate the

electronic effects of substituents on the porphyrins with the same symmetry, D , as that of 2 h

Zn(rPP(CF ) ) (48b)
3 4 (Scheme 2-7). In this comparison, the redox potential of

p-tettakis(tofluoromemyl)porphyrinato Zn(II) is investigated with other Zn(II) complexes of

selected electron-deficient porphyrins. In the first and second parts, the electronic structure of

p-teifluoromethylporphyrins is discussed by comparing the HOMO-LUMO gap of the

macrocycles with those of ^jo-tetraphenylporphyrins. As discussed in Chapter I,

section D.Za.(2), the first oxidation and reduction of a porphyrin ring correspond to the

formation of a 7t-cation radical and a 7t-anion radical.149,150 Strictly speaking, the difference

between the potentials to form Tt-cation and 71-anion radicals is not exacdy the H O M O - L U M O

gap, but the theoretical H O M O - L U M O gap agrees with the difference between the first

oxidation and the reduction potentials. 149,150 j n m e final section, the redox potentials of the

cytochrome P-450 models, P-trifluoromethylporphyrinato Fe(III) chloride complexes are

compared with those of Fe(III) complexes of other electron-deficient porphyrins to assess their

electron-deficiency and possibility as oxidation catalysts.

 136

a. Free-base P-trifluoromethyl-meso-tetraphenylporphyrins

Redox potentials of free-base porphyrins were measured under the same conditions; in

C H C 1 and with supporting electrolyte, tetrabutylammonium hexafluorophosphate (TBAPFg).

2 2

The standard potentials were obtained by the use of an internal reference;

ferrocene/ferrocenium couple.213 The experimental details are described in Chpater III.

Cyclic voltammograms of H T P P ( C F ) (46a) 2 3 2 and H T P P ( C F ) (47a)

2 3 3 are shown in

Figure 2-23. Porphyrin 46a showed the two reduction reactions and two oxidation reactions, but

the two reduction processes were not resolved well and the second oxidation process was not a

one-electron process. Porphyrin 47a showed two well-resolved, one-electron reduction and

one-electron oxidation reactions. Figure 2-24 shows the cyclic voltammograms of

H T P P ( C F ) (48a)
2 3 4 at various scan rates. A t any scan rate two clean reversible one-electron

oxidations were observed. The reduction processes differed in that the one-electron process was

always irreversible for the first electron. The electrochemical behavior of

H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 was similar to that of 48a. The reason for the irreversible reduction

process is not known. The electrochemical reduction may result in a similar change of the

macrocycle ring to that observed in the chemical reductions. Such a change led to decomposition

of porphyrin 48a and 52a (see Chapter II, section A.l.c.(2), and section A.3.b.).

For comparison, the cyclic voltammograms of (3-methylporphyrins ( H T P P ( C H ) 2 3 2 (

5 7a)
,

H TPP(CH )
2 3 3 (
5 8a)
, H T P P ( C H ) (59a)
2 3 4 are shown in Figure 2-25. The three

P-methylporphyrins showed two one-electron reduction and two one-electron oxidation

processes. In addition, porphyrin 58a and 59a showed a third one-electron oxidation process
F i
g ure 2-23. Cyclic voltammograms of (a) H T P P ( C F ) (46a) and
2 3 2

(b) H T P P ( C F ) (
2 3 3 4 7a)
. Solvent: C H C 1 , [porphyrin]^ 1 x 10 " M ,
2 2
3

Supporting electrolyte: [TBAPF ] = 1 x 10 M , Scan rate: 0.05 V / s . White

6
1

arrows indicate ferrocene/ferrocenium coupling; 0.46 V vs. S C E .

 138

2.0 1.0 0.0 -1.0 -2.0

Potential (V vs. SCE)

Fi
g ur
e 2-24. Cyclic voltammograms of H T P P ( C F ) (48a) at different scan rates.
2 3 4

Solvent: C H C 1 , [porphyrin]=5 x I O , Supporting electrolyte: [TBAPF ] = 1 x 10 M .

2 2
4
6
1
 (a)

X 10 p A

2.0 1.0 0.0 -1.0 -2.0

Potential (V vs. SCE)

Fi
g ur
e 2-25. Cyclic voltammograms of (a) H T P P ( C H )
2 3 2 (
5 7a)
,
(b) H T P P ( C H )
2 3 3 (
5 8a)
, and (c) H T P P ( C H ) (
2 35 9a)
. Solvent: C H C 1 ,
4 2 2

[porphyrin]=1 x 10 3
M , Supporting electrolyte: [TBAPF ]=1 x 10 6
_ 1
M.
Scan rate: 0.05 V / s . White arrows indicate ferrocene/ferrocinium
coupling: 0.46 V vs. S C E .
 140

that was not observed for H T P P (2a) (see Figure 1-17, p.45). Since the methyl substituents are
2

electron-releasing, the macrocycles are more electron-rich and easier to oxidize. Such a rationale

explains the increased difficulty in their reductions. The redox potentials of (3-trifluoromethyl-

and (3-methylporphyrins together with those of H T P P (2a) 2 and H T P P ( C N ) (32a,

2 X x = 2-4) 161

are summarized in Table 2-9. The redox potentials of H T P P (2a) 2 by this work show good

agreement with the reported literature values. ' 130

Thus, the cyclic voltammetry system

employed was reliable.

Tabl
e 2-9. Redox potentials of p-substituted ^?gjQ-tetraphenylporphyrins in C H C l . 2 2
a

„ , . Potential (V vs. S C E ) b

£-(3) E-(2) E°; (l)2 Eff (l) 2 Eff (2) 2 AE (1) 1/2
C

H T P P (2a)
2
d
- 1.34 1.01 -1.22 -1.56 2.23
H TPP (
2 2a)' c
f
- 1.35 e
1.02 f
-1.20 f
-1.55 f
2.22
H TPP(CF ) ( 46a) - -
d
2 3 2 1.09 -0.97 -1.28 2.06
HTPP(CF)(47a)
2 33
d
- 1.22 1.02 -0.61 -0.77 1.63
H TPP(CF ) (
4 8a) d
2 3 4 - 1.30 0.95 -0.47 - 1.42
H TPP(CF ) (CF CF )
2 3 3 2 3 (
5 2a) d
- 1.25 0.93 -0.27 - 1.20
H TPP(CH ) ( 57a )
d
2 3 2 - 1.13 0.94 -1.28 -1.60 2.22
H TPP(CH ) (5 8a)d
2 3 3 1.46 1.03 0.88 -1.29 -1.59 2.17
HTPP(CH)(59a)
2 34
d
1.40 0.94 0.81 -1.30 -1.60 2.12
H T P P ( C N ) (32a, x=2)
2 2
e
- 1.41
2.03 1.32 -0.71 -1.01
H T P P ( C N ) (32a, x=3)
2 3
c
- 1.54
1.86 1.36 -0.50 -0.61
H T P P ( C N ) (32a, x=4)
2 4 - - e
- 1.66 1.43 -0.23
"Experimental conditions: [porphyrin] = 0.5 m M ; [ T B A P F J = 0.1 M ; scan rate = 0.05 V / s ;
reference electrode = A g wire. Potentials were determined by referencing to the internal standard
of ferrocene/ferrocenium redox couple (0.46 V vs. S C E , CH Cl 2i3). E , ° ( n ) a n d E, / (n) are n th 2 2
b
2
r
2

oxidation and reduction potential respectively. ( E + E ) / 2 are reported, where E pc pa p c and E p a are
the cathodic and anodic peak potentials, respectively . AE (1) = E ° ( l ) - E, (1); H O M O - c
1/2 / 2
rc
/2

L U M O gap. This work. R e £ 1 6 1 . R e £ 1 5 6 .

d c f

The reduction potentials of the p-tiifluoromethylporphyrins (H TPP(CF )

2 3 2 (
4 6a)
,

H TPP(CF )
2 3 3 (
4 7a)
, H TPP(CF ) (
4 8a
2)
, and H T P P ( C F ) ( C F C F ) (
3 4 5 2a)
) are higher than that of
2 3 3 2 3

H T P P (2a).
2 The positively shifted reduction potentials are due to the strong electron-

withdrawing effect of - C F groups. A similar phenomenon is observed for a series of

3
 141

p-cyanoporphyrins (32a, x = 2-4). 1^1 The reduction potentials of these porphyrins are higher

than those of P-trifluoromethylporphyrins, indicating the difference in electron-witEdrawing

strength between - C F and - C N groups. Electrochemical studies regarding P-substituted

3

/W^o-tetraarylporphyrins showed the first reduction potential of the macrocycle linearly changes

with the electronic effect of a substituent and it does not depend on the structure of the

macrocycle. 1 ° 1 - 1 6 5 implies that the electronic effects of pyrrolic P-substituents should be

reflected in the difference in the first reduction potentials. The changes in the first reduction

potentials from 2a to 48a and to 32a (x = 4) are 0.75 V and 0.99 V, respectively and the

difference between 48a and 32a is 0.24 V. Similar analysis concerning the first reduction

potentials of 46a and 32a (x = 2) and 47a and 32a (x = 3) results in 0.26 V and 0.11 V,

respectively for the differences between P-trifluoromethyl- and —methylporphyrins. Thus, it is

estimated that the difference in the electron-withdrawing strength between —CF and —CN 3

groups causes approximately a 0.2 V difference in the first reduction potential. O n the other

hand, the oxidation potentials of P-trifluoromethylporphyrins 46a, 47a, 48a, and 52a are more or

less same as those of 2a, while those of P-cyanoporphyrins (32a, x = 2-4) are obviously higher

than those of 2a. As discussed in Chapter I, section D.2.£.(2), oxidation of the macrocycle is

sensitive to distortion of the macrocycle. Thus, it is probable that the electron-withdrawing

effects of —CF groups are offset by macrocycle distortion caused by the steric interaction
3

between the P-trifluoromethyl groups and the meso-pehnyl groups (We will discuss the

macrocycle distortion in detail in the analysis of an X-ray crystal structure of

Zn(TPP(CF ) ) (48b)
3 4 in section B.4.b(3)). A n estimation of the first oxidation potential of

H T P P ( C F ) (48a)
2 3 4 barring macrocycle distortion would be approximately 0.2 V higher (i.e.

~ 1.15 V) according to the analysis concerning the first reduction potentials.

 142

A n interesting observation is the H O M O - L U M O gap (AE (1) difference between the

1/2

first oxidation and the first reduction potentials, Table 2-9). This progressively decreases as the

number of —CF groups increases even when the offset of oxidation potentials is considered. A
3

similar phenomenon is also observed in a series of P-cyanoporphyrins (32a, x = 2-4). 161 O n the

other hand, such HOMO-LUMO gap contraction is not observed for a series of

p-methylporphyrins (H TPP(CH )
2 3 2 (
5 7a)
, H TPP(CH ) (
2 5 8a)
, H TPP(CH ) (
3 3 5 9a)
. Figure 2-26
2 3 4

shows the plots of the first redox potentials of p-ttifluoromethylporphyrins (46a, 47a, and 48a)

and P-methylporphyrins (57a, 58a, 59a) against the number (n) of the pyrrolic P-substituents

(-CF or —CH ). The plot ofthe first oxidation potentials of P-trifluoromethylporphyrins (•) has
3 3

a maximum at n = 2. In contrast, the first reduction potential (o) increases almost linearly. It

seems to fit a sigmoid curve better. Further discussion on this is not possible because the

potentials for n = 1 is not available for now. The deviation of the oxidation potential at n = 4

from the predicted linearity (dotted line) made by the points at n = 0 and n = 2 is 0.22 V . This

value may be reflecting distortion of the macrocycle in 48a. Even if we consider the effect of a

presumed macrocycle distortion, the difference between the first oxidation and reduction

potentials (i.e. the H O M O - L U M O gap) obviously decreases as the number of —CF groups 3

increases. The first oxidation (•) and reduction (o) potentials of p-methylporphyrins, on the

other hand, change linearly as the number of methyl groups increases and the H O M O - L U M O

gap parallels. These observations imply that the H O M O - L U M O gap contraction for a series of

P-trifluoromethyl- and P-cycanoporphyrins is due to strong electron-withdrawing effects of —CF 3

and —CN groups. This phenomenon can be also rationalized by the unique electronic
Fi
g ure2 -
2 6.R edoxp o t
e nt
i
a l
so f( a )H
2 TPP(CF 3
X)( x=0( 2 a)
,2( 46 a)
,
3( 4 7a)
,a nd4( 4 8a )
)a n d( b)H
2 TPP(CH
3
X )(x=0( 2 a )
,2( 57a)
,3 ( 58a
a
n d4( 59a )
). Sy
m bos
l in t h eg r
ap hsi
n di
c at
ed i
f
fer
e nt
e
e
lc t
r
o der eact
i
o ns; • : 1s to xi
d at
i
o nand O :1 stred uct
i
o n.
 144

structure of P-tiifluoromethylporphyrins as shown in the analysis of UV-visible and N M R

spectra. Figure 2-27 shows the energy level diagram for H O M O s and L U M O s of the four

generic metalloporphyrin classes.205 According to this diagram, as the macrocycle is reduced the

H O M O - L U M O gap progressively contracts. The gap of bacteriochlorin, in which the 1871-

electron pathway is fixed due to the reduced pyrroles in antipodal positions, displays about 60 %

of resonance compared to that of a porphyrin. P-Trifluoromethylporphyrins have a

bacterichlorin-type fixed 18TC-electron pathway (see Figure 2-16) and the distorted electronic

pathway probably leads to the narrow H O M O - L U M O gap for which strong electron-

withdrawing groups must reside on the pyrrolic P-positions of pyrroles in antipodal positions.

b. Zn(II) porphyrins

Many of the electrochemical studies of porphyrins have shown the redox potentials of

Zn(II) porphyrins. Thus investigation of Zn(II) porphyrin redox properties is advantageous for

comparison with those of other porphyrin macrocycles. In this section the redox potentials of

p-tetralds(tofluorometJiyl)-^j-o-tetj:aphenylporphyrinato Zn(II) (Zn(TPP(CF ) )) (48b)3 4 are

reported and compared with those of other selected Zn(II) porphyrin systems. Figure 2-28(a)

shows the cyclic voltammogram of Zn(TPP(CF ) ) (48b) 3 4 in CH C1 .

2 2 Unlike the cyclic

voltammetry of the corresponding free-base, two one-electron oxidations and clean two one-

electron reductions were observed. Under the same condition, redox potentials of Zn(TPP) (2b),

Zn(TPPBr ) 4 (
4 5b)
, and Zn(TPP(CH ) ) (59b)
3 4 were also measured and the redox potentials of

these porphyrins are summarized in Table 2-10 with those of other electron-deficient porphyrins

reported in the literature. In Figure 2-28(b), the first oxidation and the first reduction potentials

of P-tetrasubstituted ^.ro-tetaphenylporphyrins including Zn(TPP(CN) ) (32b, 4 x = 4) were

plotted against the 4o~ value (Table 1-3 in Chapter I, section BJ.b.(l) for o~ values for each
p p
 145

-8 r

-9 -
> — LUM0(TT*)
>.
00

-10
•••H- HOMO(TC)

O
-11

-12

Por
p hy
rn
i Chl
o r
i
n I
s obact
e r
i
o - Bact
e r
i
o -
chl
o r
i
n chl
o ri
n
Zn c
omp
e
lxe
s

Fi
g ur
e 2-27. Energy level diagram for H O M O s and L U M O s of the four
generic porphyrin classes. Adapted from ref.205.
 146

(a)

2.0 1.0 0.0 -1.0 -2.0

Potential ( V vs. S C E )

(b)
2

4a

Fi
g ur
e 2-28. (a) Cyclic v o l t a m m o g r a m o f Z n ( T P P ( C F ) )3 4 (
4 8b)
. Solvent: C H C 1 ,2 2

[48b] = 1 x 10 " M , [ T B A P F ] = 1 x 10
3
6
_1
M , scan rate: 50 m V / s . T h e white arrow
indicates ferrocene/ferrocenium couple, (b) 4 a vs. 1st oxidation ( • ) and 1st
reduction (O) potentials o f P-tettasubstituted /mo-tettaphenylporphyrinato Zn(II)
(Zn(TPP) (2b), ZnCTPP(CN) ) 4 (34b, x=4), Z n ( T P P B r )
4 (
4 5b)
, ZnCTPP(CF ) ) (
4
3 8b)
)
.
4
 147

Tabl
e 2-10. Redox potentials of |3-substituted ^ao-teteaphenylporphyrin Zn(II)
complexes in CH C1 . 2 2

Potential (V vs. SCE) a

Porphyrin
E,°; (2)
2 Ev (l)
d
2 E$(2) AE (1)1/2

Zn(TPP) (2b) b
1.12 0.80 -1.40 - 2.20
Zn(TPP) (2b) c
1.11 0.78 -1.39 -1.84 2.17
Zn(TPFPP) (4b) b
1.64 1.38 -0.99 -1.36 2.37
Zn(TPFPP) (4b) d
1.58 1.37 -0.95 -1.37 2.32
Zn(TPFPPBr ) (8b) 8
d
1.53 1.57 -0.48 -0.76 2.03
Zn(TPPBr ) (
4 5b)b
4 1.10 0.93 -1.08 -1.30 2.01
Zn(TPPBr ) (
4 5b)c
4 1.14 0.90 -1.09 -1.36 1.99
Zn(TPPBr ) (7b) 8
c
1.11 0.85 -0.85 -1.10 1.70
Zn(TPP(CF ) ) (
4 8b) 3 4
b
1.24 0.92 -0.58 -0.81 1.50
Zn((CF ) P)3 4 (
1 6b) e
- 1.44 -0.71 - 2.15
Zn(TPP(CH ) ) (
5 9b) 3 4
b
0.83 0.71 -1.50 - 2.21
Zn(TPP(CN) ) 4 (
3 2a) f
- .1.11 -0.44 - 1.55
ZnCTDCPP^O^,) (
1 5b) g
- - 0.16 - -
a
E ° (n)and E " (n) are n th oxidation and reduction potential respectively. AE (1)=
/ 2 2 1/2

E,°; (1)- E\% (1); H O M O - L U M O gap.

2

b
This work. Experimental conditions: [porphyrin]: 0.5 or 1 m M ; [TBAPF ]:0.1 M ; scan rate: 6

0.05 V / s ; reference electrode: A g wire. Potentials were determined by the internal standard of
ferrocene/ferrocenium redox couple (0.46 V vs. S C E , C H ^ h ) . 2 1 3 c
Ref.164. d
Ref.214 Values
are vs A g . A g C l . Ref.39. In benzonitrile. Ref.161. Ref.37.
c f 8

group). Since each of Zn(TPPBr ) 4 (

4 5b)
, Zn(TPP(CF ) ) (
4 8b)
, Zn(TPP(CH ) ) (
3 5 9
4b)
, 3 4

Zn(TPP(CN) ) (32b, x = 4) contains four (3-substituents, 4 a

4 p values were used instead of a p

values. As shown in the figure, the first oxidation potentials o f Zn(TPP(CH ) ) 3 4 (

5 9b)
,

Zn(TPP)(2b), Zn(TPPBr ) (
45b) 4 and Zn(TPP(CN) ) (32b, x = 4) are on a slightly curved line.
4

However, the oxidation potential for 4

8b is slightly lower than the line by about 0.2 V , which is

similar to the deviation of Figure 2-26(a). The plots of the first reduction potentials show an

interesting result. Previous studies^°2-164 h s o w e d that reduction potentials linearly changed as

the number of bromines on the P-pyrrolic positions increased. Thus we can expect that change

in the first reduction potential of porphyrins is proportional to the sum of the rj values of the p

substituents. However, as shown in Figure 2-28(b), the plot of the reduction potentials against
 148

the CT values in the series of (3-tetrasubstituted /#£ro-tettaphenylporphyrinato Zn(II) shows a

p

gentle sigmoid curve. The oxidation potentials, except for that of - C F , may also fit a sigmoid
3

curve, but the change in the oxidation potentials is too small to argue this point. Unfortunately,

the number of the data shown in Figure 2-28(b) is limited but the plots show that both oxidation

and reduction potentials are leveling off at higher 4cj values and leading to a fixed and narrow
p

H O M O - L U M O gap. This indicates that the electronic structure of the macrocycle converges

into a bacteriochlorin-type structure due to strong electron-withdrawing effects of substituents

on the antipodal pyrroles. O n the other hand, at lower 4 a values (i.e. for Zn(TPP(CH ) )
p 3 4 (
59a
))

the H O M O - L U M O gap is as wide as that of Zn(TPP) (2a). This result matches the observations

of P-trifluoromethylporphyrins by the UV-visible and N M R spectroscopies.

In order to compare P-tetealds(tiifluoromethyl)porphyrinato Zn(II) with other Zn(II)

porphyrins in Table 2-10, the first oxidation and the first reduction potentials are plotted in

Figure 2-29. As shown in Chapter I, the reduction potential reflects the electron-deficiency.

Thus, a high reduction potential of a porphyrin indicates that the porphyrin is electron-deficient.

This simple analysis ranks Zn(TPP(CF ) ) (48b) 3 4 as an electron-deficient porphyrin. It seems

more electron-deficient than porphyrin Zn(TPFPP) (4b) (see Figure 1-8, p i 1) and

Zn(TPPBr ) (7b),
8 and as electron-deficient as Zn(TPFPPBr ) (8b). 8 This latter macrocycle is well

known in the third generation porphyrin catalysts (see Chapter I, section B.Zd). For better

robustness as an oxidation catalyst, a higher oxidation potential is desired, but the oxidation

potential of Zn(TPP(CF ) ) (48b)

3 4 is the same as that of Zn(TPP) (2b). Thus, the high reduction

potential of 48b may be a good indication that it may be advantageous to activate a central metal

in porphyrin catalysts. Metal complexes such as Fe(III) or Mn(III) porphyrins may give a small
 149

L U M P of ZnTPP H O M O of ZnTPP

V V

ZnTPP (2b)

• ZnTPPBr (45b) 4
p h
^ . : z h
^ P h
sr x -fh Br

ZnTPPBr 8 (7b) b

ZnTPFPP (4b)

ZnTPFPPBr 8 (8b) c
?
h

• ZnTPP(CF ) (48b) 3 4 Ph-

FC3

ZnTPP(CH ) 3 4 (59b)

ZnTPP(CN) 4 (34b)

CN Ph
• Zn(CF3) P 4 (
1 6b) e

t\l0 2 tfC>2
\ f 0 N-
o ZnTDGPPQSlO^g (15b/ - v_
2

N y

Ar—( ^Zh(ll) >-C H CI (=Ar)6 3 2

-1 0 1
Potential (V) a

Fi
g ur
e 2-29. The H O M O (•: 1st oxidation)-LUMO (O: 1st reduction) gap of
P-substituted mro-arylporphyrin Zn(II) complexes. Potentials are in vs. S C E for
3

2b, 4b, 7b, 15b, 16b, 34b, 45b, 48b, and 59b and in vs. A g / A g C l for 8b and 12b.
Data were measured in C H C 1 except for 16b,
2 2 which was measured in benzonitrile.
b
Ref.75. Ref.214.
c d
Ref.161. R e £ 3 9 . Ref.37.
e f
 150

gain in the oxidation potential. This would be an unsatisfactory result for a robust oxidation

catalyst.

The high reduction and the low oxidation potential of Zn(TPP(CF ) ) (48b) 3 4 result in a

narrow H O M O - L U M O gap. In Figure 2-29, the numbers between the oxidation and the

reduction show the H O M O - L U M O gaps for various Zn(II) porphyrins in volts while the two

dotted lines are the H O M O and the L U M O of Zn(TPP) (2a). Obviously, the H O M O - L U M O

gaps of 48b and Zn(TPP(CN) ) (32b,

4 x = 4) are narrower than those of other electron-deficient

porphyrins. Since the H O M O - L U M O gaps of Zn((CF ) P) (16b,

3 4 n= 1) (Figure 1-8, p.ll),

Zn(TPPBr ) 4 (
4 5b)
, and Zn(TPP(CH,) ) (59b) 4 are close to that of 2a, it is obvious that both

symmetry and strong electton-witlidrawing substituents are required for the narrow H O M O -

L U M O gap. The reason for this, as explained for the free-base porphyrins, is that the

macrocycles of 48b and 32b (x = 4) presumably have the bacteriochlorin-like fixed 187t-electron,

pathway. In addition to the distorted electronic pathway of the macrocycle, offset of the

oxidation potential by the macrocycle distortion 44-146 i

m a v a j s o contribute to the narrow

H O M O - L U M O gap of 48b.

In summary, the electron-withdrawing effects of —CF groups on the pyrrolic P-positions

3

increased the reduction potentials of P-trifluoromethylporphyrins almost linearly as the number

of —CF groups increased. The first oxidation potential did not gain much from that of
3

/Wwo-tetraphenylporphyrin and a linear increase of the potential with the number of —CF groups 3

was not obtained due to the offset by a presumed macrocycle distortion. Narrowing of the

H O M O - L U M O gap was observed as the number of —CF groups increased. This is presumably
3

because the macrocycle is forced to take a distorted 1871-electton pathway just like that of
 151

bacteriocMorin by the strong electton-withdrawing effect of —CF groups on the antipodal 3

pyrroles. P-Tettakis(trifluoromethyl)porphyrin (48) may be as electron-deficient as the

porphyrins appeared in the tliird generation porphyrin catalysts such as P-octabromo-#?£ro-

tetrakis(perfluorophenyl)porphyrin (TPFPPIkg) (8) (Figure 1-8, p.11) but the oxidation potential

of 48 seems to be insufficient for a robust oxidation catalyst.

c. Fe(III) porphyrins

In the past, redox potentials of Fe porphyrins were used to discuss the activity and the

stability of the porphyrins as oxidation catalysts.45,73 j n this section redox potentials of Fe(III)

complexes of P-trifluoromethylporphyrins (Fe(TPP(CF ) )Cl (48f)

3 4 and

Fe(TPP(CF ) (CF CF )Cl

3 3 2 3 (
5 2c)
) measured by cyclic voltammetry are reported and they are

compared with those of other selected Fe(IIF) porphyrins. Table 2-11 summarizes the redox

potentials of Fe(IIi) porphyrin chloride complexes. Cyclic voltammetry measurements with

known porphyrins, Fe(TPP)Cl (2d) (Figure 1-8, p . l l ) and Fe(TPPBr )Cl (45e) 4 (Scheme 2-8)

showed that the measured values were close to the reported values. The first reduction potentials

(Fe(III/II) couple) for 48f and 52c shifted positively about 0.3 - 0.4 V from that of 2d and are as

the same as that of the wwo-tetrakis(heptafluoropropyl)porphyrinato Fe(III) chloride

(Fe((C F ) P)Cl) (16d)

3 7 4 (Figure 1-8). The Fe(III/II) couples of 48f and 52c are ranked between

the values of the second generation catalyst, Fe(TPFPP)Cl (4d) (Figure 1-8) and the third

generation catalyst, Fe(TPFPPBr )Cl (8d) 8 (Figure 1-8). Thus, redox tuning of the Fe(III) in 48f

and 52c seems to be successful for modelling P-450 compounds. However, the first oxidation

potentials of 48f and 52c are the same level of as that of 2d. This may imply that these

porphyrins will not perform as robust oxidation catalyts. The reason for the low oxidation

potentials in 48f and 52c must be the macrocycle distortion as discussed in the previous sections.
 152

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(S|
m oo ^ h cn
00 >
d
u

JJ o

e- CN t— m CN O so co 00
o m m m m
CO
SO oo cn
m
a so i n so u II

CU
PH
u
CN
m

U
a
CU (3^ T3
PH T3\- '
+H oo CN £js •d o
•d CJ
m "d
aOx m
CN -— so •d go,

o T3
PH
CJ,
U y 1
-a
PH o U
PH
m
p? P7 PQ
0 CJ 1

PH
u PP CJ, PH cj^ PH
PH '
PH PH
pT cy
CJ m

&
CN PH PH
T-H
PH PH PH" CN
C4 cu 1) cu
PH PH PH PH PH PH
H
PH PH
 153

However, as shown in Table 2-11 the first oxidation potential of one of the third generation

porphyrin catalysts, Fe(TDCPPCl )Cl (lOd)

8 (Figure 1-8), is even lower than that o f

Fe(TPP)Cl (2d) (Figure 1-8). It is not easy to predict the catalytic activity of 48f and 5
2c from the

redox properties alone. Accordingly, actual oxidation reactions have to be run to investigate the

efficacy of these Fe(III) porphyrins as catalysts.

4. Crystal structures

In this section, the X-ray crystal structures of Zn(II) complexes o f P-tetrasubstituted

^-teteaphenylporphyrins (Zn(TPPBr ) (
4 5b)
, Zn(TPP(CF ) ) (48b) and Zn(TPP(CH ) ) (
4 59b)
) 3 4 3 4

are reported. These X-ray crystal structures are very important not only to elucidate the

structures of the macrocycles but also to support discussions presented for the UV-visible, N M R

spectroscopic and electrochemical studies of the p-trifluoromethylporphyrins. These discussions

suggested a fixed 187t-electron pathway (Figure 2-16) and the macrocycle distortion as dominant

electronic and structural characteristics. O f specific interest are the steric effects of - C F groups. 3

Therefore, in the second part o f this section analysis of distortion of the macrocycle of

Zn(TPP(CF ) ) (48b) is focused.

3 4

a. Preparation of the crystals and crystallographic data.

Zn(TPP(CF ) ) (48b)
3 4 was crystallized as Zn(TPP(CF ) )-(EtOH) 3 4 3 (48b-(EtOH)) from a
3

mixture of E t O H and CHC1 . In addition to X-ray crystallography, the crystals were analyzed by
3

*H and 1 9
F N M R solution spectroscopy and elemental analysis. The 200 M H z 'H NMR

spectrum of 48b-(EtOH) in CDC1 showed that E t O H signals shifted to the higher field than
3 3

those of the normal E t O H in CDC1 3 at room temperature, suggesting a shielding effect by

porphyrin. Attempts to crystallize out Zn(TPPBr ) (45b) 4 and Zn(TPP(CH ) ) (59b) 3 4 from the

same solvent system failed due to their low solubility in E t O H / C H C 1 . Accordingly, porphyrin
3
 154

4
5b was crystallized as Zn(TPPBr )• (MeOH)• (DMF) to give the solvate 45b-(MeOH)-(DMF) by
4

slow diffusion of M e O H into the D M F solution. The compound 5

9b was crystallized as

Zn(TPP(CH ) )-(THF) -(CHCl )

3 4 16 3 04 (59b-CTHF) -(CHCl) )
16 3 04 by slow evaporation from

C H C L / T H F . These single crystals were analyzed by *H N M R solution spectroscopy and

elemental analysis as well as by X-ray crystallography. Table 2-12 shows crystallographic data.

The three Zn(II) porphyrins showed square pyramidal coordinationforthe central Zn(II)

atoms. In the crystal structure of 45b-(MeOH)-(DMF) and 48b-(EtOH), a M e O H molecule and 3

a E t O H molecule are coordinated to Zn(II) atoms, respectively. In 59b-(THF) -(CHCl ) , T H F 16 3 04

coordinated to Zn(II) and disordered structure was observedforthe axial T H F . In addition, two

different solvents, T H F and CHC1 appear to occupy the same volume 60 % and 40 % of the
3

time respectively. Details of the structures of these complexes are described in the following

section.

Tabl
e 2-12. Crystallographic datafor45b-(MeOH)-(DMF), 48b-(EtOH), and 3

59b-fTHF) , -(CHCl ) 1 6 3 ft4

45b-(MeOH)-(DMF) 48b-(EtOH), 59b-CrHF) ;(CHCl,)o,

1/

Empirical formula C H, Br N 0 Zn
4 8 5 4 5 2 C H F N 0 Zn
5 4 4 2 1 2 4 3 C54.80 ^49.2oN Zn0 . Cl
r
4 1 60

F.W. 1098.83 1088.31 897.34

space group P 1 p T P2,/n
a, A 12.257(2) 12.0428(11) 13.585(1)
b,A 13.4377(8) 13.275(2) 18.182(1)
c,A 14.387(1) 16.909(2) 18.065(2)
<x,° 83.819(2) 96.951(5)

!V 71.227(2) 108.124(2) 93.274(3)

Y,° 73.575(3) 107.354(2)

v,A 3
2151.7(3) 2383.2(5) 4454.9(6)
z 2 2 4
D c a k (g/cm )
3
1.70 1.52 1.34
u. (Mo-Ka) (cm- ) 1
43.42 6.13 6.70
T (°C) -100 ± 1 -93 ± 1 -100 ± 1
No. of observations 6086 5823 2621
R(F) 0.058 0.099 0.129
0.089 0.091 0.155
 155

b. Structure details

O R T E P views (in 30 % probability ellipsoid) of the crystal structures are shown in

Figure 2-30-45b, Figure 2-30-48b, and Figure 2-30-59b. Each figure shows the top view and the

side view. Solvent molecules for the top views and meso-phenyl groups and part of the solvent

molecules for the side views were omitted for clarity. Selected bond lengths and bond angles for

the shown structures are summarized in Table 2-13. Structural data for

Z n ( T P P ) ( H 0 ) (2a-(H 0)) 16
2 2
2
a r e also listed in the table for comparison. Some designations

used in Table 2-13 are shown in the molecular diagram in Scheme 2-10.

R = H (2b)
= Br (45b)
= C F (48b)
3

= C H (59b)
3

S
che
m e 2-10. Atom designations used in Table 2-13.

(1) Core si%e, Zn displacement, and axial coordination

Coordination around Zn(II) in complexes 45b(MeOH)-(DMF), 48b-(EtOH), and 3

59b-(THF) -(CHCl ) is penta-coordinate square pyramidal. This structure is common for

16 3 04

Zn(II) porphyrins. ! ^ In complexes 45b, 48b, and 59b, the Zn(II) atoms are displaced by 0.277,
2

0.325, and 0.234 A from the least-square plane through the four porphyrin nitrogen atoms ( N 4

plane), respectively. These values are larger than the 0.173 A reported for

Zn(TPP)-(H 0) (2a-(H 0)). 16 The macrocycle core sizes (N—Cr, where Ct is the centroid of
2 2
2

the four nitrogen atoms. Table 2-13 for the details.) of Zn(TBBBr ) (
4 5b)
, Zn(TPP(CF ) ) (
4 4 8b)
, 3 4
 156

Fi
g ur
e2-
3 0-
4 5b. X-ray crystal structures of 45b- (MeOH)- (DMF). The axial ligand and
the solvent molecule for the top view and the meso-xphenyl groups for the side view
were omitted for clarity.
Fi
g ur
e2-
3 0-
4 8b. X-ray crystal structures of 48b- ( E t O H ) . The axial ligand and
3

the solvent molecules for the top view and the meso-phenjl groups and solvent
molecules for the side view were omitted for clarity.
 158

Fi
g ur
e2-
3 0-
5 9b. X-ray crystal structures of 59b- (THF), - (CHC1 ) . The axial ligand and
6 3 04

the solvent molecules for the top view and the meso-phenyl groups and solvent molecules for
the side view were omitted for clarity.
 159

Tabl
e 2-13. Core size, selected bond lengths and bond angles.
Zn(TPPBr ) 4 ZnCrPP(CF ) )3 4 Zn(TPP(CH ) ) Zn(TPP) b

Selected bonds"
3 4

(45b) (48b) (59b) (2b)

N—Ct, N' C f Core size (A) d

N1 Ct 2.097 2.105 2.076

N3 Ct 2.090 2.108 2.076
2.043
N2 Ct 2.012 1.976 2.013
N4 Ct 2.006 1.949 2.010
Bond length (A)
Zn-O 2.108(MeOH) 2.110(EtOH) 2.182(THF) 2.228(H Q) 2

Zn-N, Zn-N ,c

Zn1-N1, Zn1-N3 2.121,2.109 2.130,2.108 2.091, 2.092

2.050
Znl-N2, Znl-N4 2.030, 2.021 2.008, 1.997 2.024, 2.020

N-Ca, N'-C 'a

c

N1-C1, N1-C4 1.371, 1.374 1.379, 1.378 1.356, 1.385 1.374,1.369

N3-C11,N3-C14 1.383, 1.371 1.365, 1.374 1.375, 1.384
N2-C6, N2-C9 1.372,1.369 1.382,1.380 1.380,1.380
N4-C16, N4-C19 1.365,1.375 1.384,1.378 1.379,1.368
CcrCp, C ' - C p '
a
c

C1-C2, C4-C3 1.451, 1.449 1.462, 1.445 1.453, 1.447 1.441,1.443

C11-C12, C14-C13 1.448, 1.446 1.439, 1.459 1.468, 1.454
C6-C7, C9-C8 1.445,1.450 1.445,1.445 1.454,1.449
C16-C17, C19-C18 1.449,1.439 1.446, 1.464 1.443,1.470
Cp-Cp, C p ' - C p ' c

C2-C3, C12-C13 1.357, 1.344 1.371, 1.366 1.382, 1.369

1.341
C7-C8, C17-C18 1.342,1.346 1.335,1.337 1.337,1.358

C1-C20, C4-C5 1.408, 1.411 1.424, 1.404 1.428, 1.417

C11-C10, C14-C15 1.411, 1.405 1.445, 1.414 1.408, 1.423
1.405
C19-C20, C6-C5 1.405,1.400 1.386,1.401 1.394,1.394
C9-C10,C16-C15 1.395,1.405 1.407,1.392 1.391,1.374
Selected angles 3
Bond anj les 0?

N-Zn-N, N ' - Z n - N '

N1-Zn1-N3 163.9 166.8 165.9
170.3
N2-Znl-N4 165.4 156.8 168.1

CcrN-Ca, Ca'-N-Ca"-'
C1-N1-C4,C11-N3-C14 108.5, 107.8 108.2, 108.1 105.2, 106.6
106.8
C6-N2-C9, C16-N4-C19 107.1,106.2 106.3,107.4 106.9,108.0

(continued)
 160

Tabl
e 2-13 (continued)
Zn(TPPBr ) 4 Zn(TPP(CF ) ) ZnCTPP(CH ) ) Zn(TPP) b

Selected angles"
3 4 3 4

(45b) (48b) (59b) (2b)

Bond an gles 0

CyCVA/, C ' - C ' - N ' p a

e

C2-C1-N1, C3-C4-N1 108.7, 107.9 108.7, 108.1 111.9, 110.9

C12-C11-N3, C13-C14-N3 108.0, 108.5 109.4, 108.1 109.8, 109.8
109.3
C7-C6-N2, C8-C9-N2 108.9,109.2 109.1,109.3 109.1,108.6
C17-C16-N4, C18-C19-N4 110.0,109.8 108.3,108.5 108.9,108.6
CorCp-Cp, C '-Cp'-Cp'
a
c

C1-C2-C3, C4-C3-C2 106.8, 108.1 106.2, 108.1 105.6, 106.3

C11-C12-C13, C14-C13-C12 107.9, 107.6 106.8, 107.2 106.4, 107.2
107.5
C6-C7-C8, C9-C8-C7 107.8,107.0 107.7,107.5 107.1,108.3
C16-C17-C18, C19-C18-C17 106.7,107.3 108.6,106.9 107.9,106.6
CcrCmeso~Cpby CQ?-Cmeso-Cph ^ 0

C1-C20-C , C4-C5-C pU 119.1, 118.6 121.0, 117.6 119.3, 117.7 ph1

C11-C10-C ,C14-C15-C 118.3, 118.6 118.3, 121.8 118.4, 117.2

hh2 hhi
117.2
C19-C20-C , C 6 - C 5 - C
ph4 phl 115.4,116.4 114.7,117.4 115.7,115.8
C9-C10-C , C16-C15-C
nh2 oh3 116.3,116.0 117.8,113.2 115.4,117.3
Ca-Cmeso-Ca' 6

C1-C20-C19, C4-C5-C6 125.5,124.8 124.3,124.5 124.9,126.5

N.A.
C9-C10-C11,C14-C15-C16 125.4,125.4 123.7,125.0 126.2,125.5
C -Cp-R *
a
e

C1-C2-R 129.5 128.6 129.6

C4-C3-R 128.7 124.2 129.5
C11-C12-R 129.6 125.7 127.6
C14-C13-R 129.6 129.3 128.3
a
See Figure 2-30-45b, 48b and 59b for atom designations. Ref. 216. Ct is the centroid of the b c

four nitrogens. d — [^(x^xj + b (y -y^) +c (^ -^ ) + 2bc-cosa{y j^)(^-t^) +

d
Calculated using
2 2
x
2 2
J 2
2
r

2ca-cosR(^-^)(x x^) +2ab-cosy{x x^){y j )] , where d is the distance between coordinates

r r r 2
i/2

( uji, Ki)
x
( i,j2, a
Scheme 2-10 for N , N ' , C , C ' , Cp, Cp', C , and C designations.
n d x e S e e
a a mta p h

f
Cph,: C21 for 45b, C25 for 48b and 59b, C : C27 for 45b and C31 for 48b and 59b, C : C33 p h 2 p h 3

for 45b and C37 for 48b and 59b, C : C39 for 45b and C43 for 48b and 59b. R: Br for 45b, p h 4
8

C F for 48b, and C H for 59b.

3 3

and Zn(TPP(CH ) ) (59b) 3 4 in the direction of P-substituted pyrroles (values in this direction are

reported in italic in Table 2-13; N- • -Ct (average) = 2.048, 2.106, and 2.076K respectively) are

obviously larger than those in the direction of non-substituted pyrroles ( N ' - C t

(average) = 2.009, 1.962, and 2.012 A respectively) and the core sizes in the direction of non-
 161

substituted pyrroles of 45b, 48b, and 5

9b are smaller than that ( C t - N (2.043 A)) o f the

macrocycle in Zn(TPP)-(H 0) (2a-(H 0)).

2 2
216
The largest Zn(II) displacement from the N 4

plane in 4
8b may be due to the smallest N---Ct values in the direction of non-substituted

pyrroles.

Although the axial ligands for the complexes in Table 2-13 are different, the donor atom in

all cases is oxygen. Thus, comparison of Z n - O distance may provide a rough measurement for

the electron-deficiency of the porphyrins. The Z n - O distances of 45b-(MeOH) (2.108 A) and

48b-(EtOH) (2.110 A) are significandy shorter than the 2.228 A o f Zn(TPP)-(H 0)2

(2a-(H 0)) or the 2.226 A of Zn(OETPP)-(MeOH) (30) (see p.43 for 30) and comparable
216 1
4
7
2

to the 2.092 A of Z n f T P P F ^ t H p ) (12b-(H0)) (Figure 1-8, p . l lfor1

2
4
1
2b)
, indicating electron-

deficiency of the macrocycles of 4

5b and 48a.

(2) Effects of antipodal B-substitution

Antipodally P-substituted porphyrins show unique structural profiles. Firsdy, Z n - N

distances (or the core sizes) are longer in the direction of P-substituted pyrroles (see Table 2-13)

than in the direction non-substituted pyrrole. In the reported structural studies of antipodally

or l-Melm) (63), .
2
192
20
substituted porphyrins such as Ni(TPP(CN) )-(L) (L=py
4 2

(Fe(TPPBr )) 0 (64), or Fe(TPPBr )Cl (45e), similar differences

1
9
2 1
9
1
4 2 4 in Z n - N distances

between the p-substituted and non-substituted directions were observed. The bond weakening
 162

of Z n - N in the P-substituted direction due to electron-wimdrawing effects of the substituents is

the rationale for such observations.1^1,219 However, a recent r e v i e w ^ f crystal structures of

2
Q

antipodally P-substituted /^.ro-arylporphyrins suggested there are considerable distortions of the

macrocycle cavity due to both electronic and steric effects of the substituents. As shown in

Figure 2-31, due to the steric interaction between the P-substituents (R and R) or R and meso-

phenyl groups, the phenyl groups are pushed away from the R groups. The macrocycle expands

in the direction of the P-substituted pyrroles and contracts in the direction of the non-substituted

pyrroles. The analysis shown in Figure 2-31 is essential to rationalize a similar observation

regarding the Z n - N distances in Zn(TPP(CH ) ) (59b) 3 4 (Table 2-13) which cannot be explained

by the electronic effects of electron-releasing — C H 3 groups. The steric interaction of the

substituents seems to be reflected on the longer Cp-Cp lengths (C2-C3 > C7-C8, Table 2-13) in

Zn<TPP(CF ) ) (48b)
3 4 and Zn(TPP(CH ) ) (59b)
3 4 due to the repulsion between the bulky pyrrolic

P-substituents; the effective van der Waals radius of the - C F group is 2.2 3

A 126
and that of - C H ,

group is 1.8 A ^ 6 . The C2-C3 and C12-C13 lengths in 48b

2
and 59b are significantly longer than

those in Zn(TPP) (2a). In contrast, significant differences in Cp-Cp (C2-C3 vs. C7-C8) bond

lengths were not observed for Zn(TPPBr ) (

4 5b)
. The van der Waals radius of Br (1.95 A ) ^
4
2 3
is

nearly as large as that of - C H , but the Cp-Br bond length in 45b

3 (1.87 A, not shown in

Table 2-13) is much longer than that of Cp-CH in Zn(TPP(CH ) ) (59b)

3 3 4 (1.54 A). The difference

is due to the longer Cp-Br lengths. This reduces Br-Br contacts. The C -C -C a ims ph angles

(Table 2-13) show the steric interaction between meso-phenyl groups and the pyrrolic P~

substituents; wider angles were observed in the direction of the P-substituted pyrroles.

Comparison of Cp-Cp lengths in various antipodally P-substituted porphyrins is summarized in

 N ~ W Steric interaction

Figure 2-31. Schematic illustration of the steric effects of antipodal

(5-substituents and meso-phenyl groups on the macrocycle of
P-tetrasubstituted OT^o-tetraphenylporphyrin.
 164

Table 2-14. In the metalloporphyrins of P-tetrabromo-^Jo-phenylporphyrins 45b and 45e, the

difference between the two Cp-Cp lengths is not obvious. The longer Cp-Cp bonds in the

direction of P-substituted pyrroles in 59b and 63 suggest that the bond elongation was caused by

either steric or electron-withdrawing effects. In Zn(TPP(CF ) ) (

4 8b)
, it is likely that elongation 3 4

of Cp-Cp bonds occurs due to both effects. The electron-withdrawing effect of —CF group 3

Tabl
e 2-14. Cp-Cp bond lengths in antipodally P-tetrasubstituted
^?gjQ-tetraphenylporphyrins.
Cp-Cp length (A)
Porphyrins P-substituted P-non-substitued Reference
direction direction
Zn(TPPBr ) (45b)
4 1.35 1.34
fFe(TPPBr )]Cl (45e)
4 1.36 1.35 b

Zn(TPP(CF ) ) (48b)
3 1.37
4 1.34
Zn(TPP(CH ) ) (59b) 3 1.38 4 1.35
Ni(TPP(CN) ) (63) 4 1.37 1.34 c
- d

Zn(TPP) (2b) - 134 e

a
This work. Ref.191. Ref.219. Ref.220. Ref.216.
b c d e

presumably leads to a low electron density of the bonds between the pyrrolic P-carbons where

the substituents are attached. This Cp-Cp elongation in 48b may direct the 187t-electron to avoid

resonance through those double bonds.

(3) Macrocycle distortion

Investigation of macrocycle distortion of P-teti:altis(tjifluoromethyl)porphyrin is important

in order to rationalize the UV-visible, N M R spectra, and electrochemical data of the porphyrin.

Here, distortion of the macrocycle of Zn(TPP(CF ) ) (48b)

3 4 is compared with that of

Zn(TPPBr ) (45b)4 and Zn(TPP(CH ) ) (59b) 3 4 and then the mechanism of the distortion is

analyzed.
 165

Figure 2-32 shows the degree of distortion in the macrocycles of 45b, 48b, and 59b. The

numbers in the porphyrin structures indicates the deviation (in 0.01 A) of each atom from the N 4

mean plane. We can imagine the N plane to be on the page of the figure for the porphyrin
4

structures in the left column. The atoms with positive values are above the page in the porphyrin

structures, while atoms with negative values are below the page. The figures beside the porphyrin

structures show the skeletal deviations of the 24 core atoms of the macrocycles from the N 4

mean plane. As indicated in Figure 2-32(a), (b), and (c), for all the three macrocycles, pyrrole

rings are alternately up and down relative to the N mean plane and thus the macrocycles are 4

saddle-distorted (for general modes of porphyrin distortion refer to the references. 18,145) -ph e

averages of the absolute values of pyrrolic P-carbon displacements are 0.40, 0.79, and 0.52 A in

45b, 48b, and 59b, respectively. Distortion of the macrocycle observed in 4

5b and 5
9b is very

similar to that in Z n f T P P F ^ t H p ) (12b-(H0)) (see Figure 1-8, p. 11 for 1

2b) which showed
2
4
1

the saddle distortion and the average value, 0.49 A, of pyrrolic P-carbon displacement. In fact,

crystal structures of a four-coordinate Zn(TPPBr ) (

45b) 4 shows a planar porphyrin

macrocycle.221 Thus, it is very likely that the distortion o f Zn(TPPBr ) (

4 4 5b)
,

Zn(TPP(CH ) ) (
5 9b)
, and Zn(TPPF ) (
3 4 12b) is due to the five-coordinate Zn(II), which is
8

displaced by 0.23-0.28 A from the N plane. The 0.79 A displacement of pyrrolic P-carbons on
4

average in Zn(TPP(CF ) ) (
48b) is obviously larger and this indicates the severe distortion of the
3 4

macrocycle itself. Comparison of the rms (root-mean-square) values (Figure 2-32), which are the

average deviations of the 24 core atoms from their least squares plane, also shows the severe

distortion in the macrocycle of 48b. The van der Waals (vdW) radius of fluorine is 1.35 -

1.47 A 1 2 3
' 1 2 6
, which is close to 1.1-1.3 A of hydrogen. 1 2 3
However, the size of - C F is
3

estimated to be 2 . 2 A . 1 2 6
. T h e vdW radius of - C F 3 is estimated as 2.69-2.81 A
 166

(a) ZnCTPPBr )
4

(b) ZnCTPP(CF ) ) 3 4

(c) ZnCTPP(CH ) ) 3 4

Fi
g ur
e 2-32. Perpendicular atomic displacements of Z n porphyrins (a) 45b, (b) 48b,
and (c) 59b, relative to the N mean plane. The numbers in the porphyrin structures
4

on the left column are the distances in 0.01 A units. The figures on the right column
display the skeletal deviations of 24 core atoms of the porphyrins from the N mean
4

plane. • indicates the pyrrolic P-carbons bearing substituents. The rms values show
the average deviation of the 24 core atoms from their least squares plane.
 167

from the crystallographic data of 48b; the vdW radius of —CF = 1.34 A(average C - F distance)
3

+(1.35 to 1.47 A) (vdW of F). Thus, it is probable that - C F is 3 much larger than

- C H (vdW = 1.8 - 2.0 A)123,126

3 a n ( j s t e r i c interactions among substituents are expected. As

observed in the top view in Figure 2-30-48b, two meso-phenyl groups (C25-C30 and C31-C36)

seem to be extremely twisted due to the steric interaction with-CF groups. The average of the
3

torsion angle made by C ^ ( C 2 6 or C30)-C25-C5-C (C4 or C6) is 54.4° and similarly 52.1° for
a

the other extremely twisted phenyl ring (C31-C36). Interestingly, two other phenyl rings (C37-

C42 and C43-C48) are almost orthogonal to the best plane of the porphyrin macrocycle (the

corresponding torsion angles are 85.2 and 80.2°, respectively). Instead; the compensation for it

seems to be made by pushing the - C F groups away from these phenyl groups (C37-C42 and
3

C43-C48). SmaU C4-C3-R (R=C22) and C11-C12-R (R=C23) angles (see Table 2-13) are

indications of the interaction between the phenyl groups (C37-C42 and C43-C48) and the - C F 3

groups that eventually forces the two phenyl rings (C25-C30 and C31 and C36) to rotate. This

structural relationship is clearly shown in Figure 2-33(b), which is a part of the crystal structure

of Zn(TPP(CF ) ) (48b)
3 4 projected from the direction indicated by the arrow in the stick model of

the top view of the molecule (Figure 2-33(a)). The steric interaction between the phenyl (C43-

C48) and - C F (F1-F3) determines the orientation of the - C F so that no F of F1-F3 is pointing
3 3

at the face of the phenyl ring. This orientation makes the F3 point at the adjacent - C F (F4-F6), 3

which orients so that F3 points between F4 and F5. Similarly the orientation of the - C F (F4-F6) 3

shifts the position of the phenyl ring (C25-C30) to minimize the steric interaction. In addition,

the negative interactions between the 7t-cloud of the phenyl rings and the - C F groups may be 3

the driving force for the severe distortion of the macrocycle. A n electrostatic repulsion between

the electronegative fluorine and the 7t-electrons is k n o w n . 2 2 2

The distance from the center
 168

Fi
g ur
e 2-33. Orientations of phenyl and CF 3 groups in 48b. (b) shows
a projection of a part of the crystal structure, 48b shown by stick model (a),
from the direction indicated by the arrow.
 169

of the carbon atom to the plane of the adjacent phenyl ring would be approximately 3 A, if it

were not for steric interactions. Since the half thickness of benzene is 1.85 A 1 2 3
and the vdW

radius of —CF is at least 2.2 A ^ " , a strong electronic repulsion between these two groups is
3
2

expected. The average torsion angles made by the C o r t h o -C -C „„-C are 68.4, 78.2, 76.8, and
ph OT a

72.9° in Zn(TPPBr ) (45b) 4 and 75.9, 67.6, 71.5, and 71.3° in Zn(TPP(CH ) ) (59b) 3 4 and none of

the phenyl groups in 4

5b and 5
9b is severely twisted. Figure 2-34(b) shows the orientations of

phenyl and C H groups featured in a part of the crystal structure of 59b.

3 There is no such strong

interaction between the phenyl and C H groups as that observed in Zn(TPP(CF ) ) (

3 4 8b)
. 3 4

(4) Orientation of the axial ligand

A n interesting feature of the crystal structure of 48b-(EtOH) is the orientation of E t O H

3

molecules to the macrocycle distortion. A s shown in Figure 2-30-45b and Figure 2-30-59b, in

45b-(MeOH)-(DMF) and 59b-fTHF)j.-(CHCl3) axial ligands are coordinated to Zn(II) on top

6 a4

of the bow-like shape created along the direction of antipodal P-substitution (Scheme 2-11(a)).

O n the other hand, in 48b-(EtOH) (Figure 2-30-48b) an ethanol is coordinated to Zn(II) in the
3

bow-like shape along the direction with - C F groups (Scheme 2-11 (b)). Interestingly, as shown in
3

Figure 2-30-48b, the axial ethanol is hydrogen bonded to the second ethanol (HI 0 2 (1.90 A)),

whose methylene hydrogen (H32) has a non-bonding contact with F9 (H32 F9 (2.71 A)). The

third ethanol (not shown in the figure) is also hydrogen-bonded to the second

ethanol (03 H31 (2.03 A), where 0 3 is the oxygen atom in the third ethanol and H31 is

hydroxyl hydrogen of the second ethanol). There were also many other H F nonbonding

contacts within 3 A between solvent ethanols, P-pyrrolic hydrogen, or phenyl ring hydrogen and
 170

Fi
g ur
e 2-34. Orientations of phenyl and C H 3 groups in 59b. (b) shows
a projection of a part of the crystal structure, 59b shown by stick model (a),
from the direction indicated by the arrow.
 171

R=Br, C H
=porphyrin macrocycle
3

L=MeOH, T H F

(a) (b)

S
che
m e 2-11. Schematic representations of macrocycle distortion and axial
coordination in (a)Zn(TPPBr)(45b)• (MeOH) and Zn(TPP(CH))(59b)-(THF) and in
4 3 4

(b) Zn(rPP(CF ) ) (48b) • (EtOH).

3 4

-CF 3 moieties across the different porphyrin units. Intermolecular c _ p -

5+ 5
a n d "C-H
5 8 +
bond

dipole interactions or C-H—F-C hydrogen bonding is known. 26

1
Unfortunately, these

non-bonded contacts are so complicated in this porphyrin system that they cannot be pictured in

an appropriate way.

In summary, crystal structure analysis of three zinc complexes of P-teteasubstitued meso-

tetraphenylporphyrins showed elongated macrocycle cavities due to the substituents on the

pyrrolic P-positions of antipodal pyrroles. Elongation of the macrocycle was reflected in

different Z n - N distances (or core sizes) in the directions of P-substituted pyrroles and of non-

substituted pyrroles. The Cp-Cp bonds in the P-substituted direction can also be stretched due to

the strong election-withdrawing and/or steric effect of the P-substituents. The structure analysis

also revealed slightly distorted macrocycles of Zn(TPPBr ) (45b)

4 and Zn(TPP(CH ) ) (59b) 3 4 and

very distorted macrocycle of Zn(TPP(CF ) ) (

4 8b)
. These observations support the results
3 4

obtained in UV-visible spectroscopy and electrochemistry. Electron-deficiency is reflected on the

shortening of Z n - O distances in 45b-(MeOH) and 48b-(EtOH). A n interesting result to be noted

 172

is that axial ethanol as well as one of the two solvated ethanols are found in a pocket created by -

C F groups and the macrocycle distortion. This could be due to the high affinity of - C F moieties
3 3

to the hydrocarbon moieties for ethanol and may be an advantageous property for hydrocarbon

oxidation using the Fe(III) complex of this porphyrin as a catalyst.

5. Spectrophotometric titration

In Chapter II, section B.3., the electron-deficiency of fi-tnQuoiomethyl-meso-

tetraphenylporphyrins was evaluated by the analysis of redox potentials measured by cyclic

voltammetry. In section B.Za. describing NMR spectroscopy experiments of

(3-tos(trifluoromethyl)porphyrin H T P P ( C F )
2 3 3 (
4 7a)
, it was shown that exchange of N H protons

of the porphyrins with the proton of residual water easily occurs. This phenomenon may be

related to the lower pK, value for the first deprotonation of the free-base porphyrin compared to

non-electron-deficient porphyrins such as H T P P (2a) 2 (Figure 1-8, p . l l ) . Given this, it became

essential to estimate the piC, of P-trifluoromethylporphyrins. In the first part of this section,

spectrophotometric titrations of the free-base of p-tetrakis (trifluoromethyl) -meso-

tetraphenylporphyrin (H TPP(CF )
2 3 4 (
4 8a)
) with D B U and E t N in C H C 1 are shown. In the
3 2 2

second part, spectrophotometric titrations of Co(TPP(CF ) ) (48e) 3 4 with pyridine (Py) and

imidazole (lm) are shown. There are a few reports of determination of Py and l m binding

constants of Co(II) porphyrins. 177-180 These include some electron-deficient porphyrins.

Comparison of the binding constants with other electron-deficient porphyrin systems was

allowed by analysis of the titrations using 48e. Thus, this section provides additional information

regarding the electron-deficiency of P-tetralds^fluoromethy^-OTWO-tettaphenylporphyrin.

 173

a. Titration of 48a with strong organic bases in CH C/2 2

(1) Titration with DBU

Figure 2-35 shows the results of the spectrophotometric titration of 48a with D B U in

CH C1 . Figure 2-35(a) shows an isosbestic spectral change for the first deprotonation. The
2 2

arrows indicate the direction of the change of the absorption peaks. The color of the solution

changed from golden-yellow for the free-base to weak orange for the first deprotonated species.

This colorimetric change stopped at [DBU] = 4.5 x 10" M. After the first deprotonation, the 2

second deprotonation was attempted using neat D B U (Figure 2-35 (b)). The further colormetric

change was observed, but the spectral change did not stop for the second end point. Assuming

that the spectrum at [DBU] = 4.5 - 5.4 x 10 2

M is that of the porphyrin monoanion, the pK

difference between H P (P stands for porphyrin dianion) and DBUH (protonated D B U ) was
2
+

determined (see Experimental section in Chapter TV). The results were analyzed based on the

absorbance change at 463 and 513 nm (s™' =9.34 x 10 , s™~ =3.22x 10 , S ^ J =8.78 x 10 , and 4 4 3

e
M3 =
3.72 x 10 M "'xm"') ). The logarithmic analysis of the first colorimetric change gave a
4

straight line with a slope of 1.1 and the intercept of 2.9 as the pK value for the reaction, H P + 2

D B U <^ H F + D B U H +
(Figure 2-36). The p X i s indeed the difference between the pK\. (pK, nv

of H TPP(CF ) ) and p K
2 3 4 D B U (pK, of D B U ) (see Chapter IV, Section C , Spectrophotometric

titrations.); pK = ApiC, = p.K p - p X H2 D B U . The pK^ of D B U in M e C N was determined as

24223,224 a n d ^

in H 0 was estimated as 1 4 .
2
2 2 3
Unfortunately, the pK, of D B U in C H C 1 is
2 2

not known. Thus, we can only compare the acidity of porphyrins by using D B U as an anchor.

Woller and DiMagno determined the pi<Q difference (ApiCj between electron-deficient

porphyrins H T P P F (12a), H T P F P P F (13a) (Figure 1-8, p . l l ) and D B U in C H C 1 by the same

2 8 2 8 2 2

method and found that the N H in 12a and 13a were less acidic than protonated D B U by 3.9 and
 300 400 500 600 700 800 900 1000
Wavelength (nm)

Figure 2-35. UV-visible spectral change in titration of H T P P ( C F ) (48a)

2 3 4 with
D B U in C H C 1 . [48a]
2 2 = 1.24 x 10" M . (a) The first deprotonation at [DBU] =
5

0 - 5.4 x 1 0 M . N o spectral change between 4.5 x 10" and 5.4 x 10" M .

_2 2 2

(b) The spectral change at [DBU] = 5.4 x 10" ~ 1.5 M .

2
 1
Log([H P]/[HP-]) = 1.1 x log ( p B U H ] / [ D B U ] ) + 2.9
2
+

-2 H 1 1
:
1
-4 -3 -2 -1
log [H P]/[HP-]
2

Fi
g ur
e 2-36. Logarithmic analysis of the spectral data for the addition of D B U to
H T P P ( C F ) (48a)
2 3 4 in C H C 1 . pK = pK -pK ;
2 2 H2V mv pK mv and pKDm are pK a

of 48a and D B U H , respectively.

+
 176

0.2 units respectively and 12a was at least 1000 times more acidic than H T P P (2a) 2 (pK, for

2a > 19).36 The ApK, of 2.9 for 48a proves that this porphyrin is indeed an electron-deficient

porphyrin.

(2) Titration with Et N 3

A similar titration was performed on 48a in C H C 1 with taethylamine. Figure 2-37 shows
2 2

the UV-visible spectral change for the titration. The spectral change occurred isobestically but in

a different way from the titration with D B U . N o further spectral change occurred after

[taethylamine] == 1.43 x 10 1
M . The final spectrum has only one broad band at 420 nm

(s = 7.45 x 10 M 4 _ 1
cm ). The color of the final compound was orange. This orange color
_1

slowly fades away in C H C 1 solution at room temperature. When 6 x l O ^ M of H T P P ( C F )

2 2 2 3 4

was treated with 0.29 M of taethylamine in CH C1 , the initial peak intensity at 420 nm of the
2 2

orange compound dropped to 40% in a few days at room temperature and no other new peaks

were observed. The UV-visible spectrum of the orange compound was the same as that in

Figure 2-4; the porphyrin is presumably reduced by E t N . 3

b. Titration of Co(TPP(CF ) ) } 4 (48e) with pyridine and imidazole

Binding constants for pyridine (Py) and imidazole (Im) coordination to

Co(TPP(CF ) ) (48e)
3 4 were also measured in C H C 1 by spectrophotometric titration.
2 2

The UV-visible spectra given in Figure 2-38 show the change for the first step of pyridine

addition to 48e. The spectral change showed six isobestic points and is very similar to the change

for the first pyridine coordination to Co(TPP(CN) ) in C H C 1 . ^ 4 2 2

9
The second coordination was

very slow and thus titration was not possible, though spectral changes occurred with isobestic

points. This result is shown in Figure 2-39. When 40,000 eq. of pyridine was
0.7

350 450 550 650 750 850 950

Wavelength (nm)

Fi
g ure 2-37. UV-visible spectral change in titration of HTPP (
C F )
(4
28a) 3
4

with E t N in C
3 HC1 . [48a] = 5.74 g 10 " M . [Et N] = 0 - 4.30 x 10 M .
2 2
6
3
4
 178

0.0 H 1 1 1 1
350 400 450 500 550
Wavelength (nm)

Fi
g ur
e 2-38. Titration o f C o C T P P ( C F ) ) (48e)(8.60 x 10 ~ M ) i n C H C l w i t h pyridine
3 4
6
2 2

at 25.0 ° C : spectral change at (a) 350 - 850 n m and (b) the Soret b a n d region during the
transition between 4- and 5-coordinate cobalt, [Py] =0 - 2.76 x 10 " M . 3
 350 450 550 650 750 850
Wavelength (nm)

Fi
g ur
e 2-39. Spectral changes in the pyridine addition to Co(TPP(CF ) )- (Py) 3 4

(48e- (Py)) (8.60 x 10 " M) in C H C 1 at 25.0 ° C . [Py] = 2.76 x 10 " - 3.40 x 10

6
2 2
3 4
 180

added to the Co (II) porphyrin, a slow change of the spectrum with time was noticeable. It took

about 15 days at 25 °C for the reaction to reach the equilibrium. Similarly, a slow second ligand

addition reaction was observed using imidazole at 25 °C. For Co(TPP(CN) ), CofTPPFg), and 4

Co(TPFPPF ) such a slow reaction for the second ligand addition was not reported and the
8

binding constants (X, and K^) were given.179,180 -p^e reason for the slow reaction might be the

sterically very crowded porphyrin peripheral of Co(TPP(CF ) ) 3 4 (

4 8e)
. It was shown in the

analysis of the crystal structure of Zn(TPP(CF ) ) (48b) that macrocycle distortion occurs due to
3 4

the interaction between the phenyl rings and - C F groups. Coordination of first Py (or lm) to
3

four coordinate 4
8e may result in a similar structure that was observed for

Zn(TPP(CF ) )-(EtOH) (48b-(EtOH)) (Figure 2-30-48b) with Co(II) deviated from the N
3 4 3 3 4

plane. As discussed in section B.4., the severely saddle-distorted macrocycle of 48b-(EtOH) is a

necessary structure to minimize the interaction between the phenyl and —C F 3 groups. The

second axial coordination to the five-coordinate Co(II) complex would have to by necessity

move the Co(II) into the centroid of the four pyrrolic nitrogens. The two axial nitrogens and the

change from the five-coordinate to the six-coordinate complex may also require rearrangement

of the peripheral substituents. Since the steric interaction among the peripheral substituents is

severe in the P-tetraltis(trifluoromethyl)-wwo-tetiaphenylporphyrin ligand (chapter II,

section B.4.), fast change from the five- to six-coordinate complex may be encumbered. The

reason that the logJ<C for Co(T((?-OCH )PP) (43) 1^8

2 3 w a s n o t g i n may be a too weak binding of
v e

the second ligand. Thus in order to observe binding of the second ligand, an electron-deficient

and planar macrocycle ligand is necessary.

 I
181

Fi
g ur
e 2-40. Logarithmic analysis of the spectral data for the addition of
pyridine to Co(TPP(CF))(48e) in C H C 1 . The pyridine addition step was
34 2 2

monitored at 440 nm. A , A , and Ay are absorbances without pyridine,

0

at each titration point, and at the final point, respectively.

 182

Logarithmic analysis (Hill's plot) - of the spectrophotometric data for the first pyridine
22 5

addition is shown in Figure 2-40. The analysis gave a binding constant of log iC, = 4.2. A similar

experiment with imidazole gave log iC, = 7.5. These results are listed in Table 2-15 with reported

Tabl
e 2-15. Binding constants of Co(II) porphyrins for base binding in in CH^CLj.
Porphyrin Base log K x log K 2 Reference
(48e)
a
Co(rPP(CF ) ) 3 4 Py 4.2 -
a
Im 7.5 -

CoCl>-OCH )PP) 3 (43) Py 2.68 - 158

Im 3.15 - 158
1-Melm b
3.37 - 158
Co(TPP(CN) ) 4 (34c) Py 4.2 -0.35 179
CofTPPFg) (12h) Py 4.3 -0.08 180
Co(TPFPPF ) (14h)8
Py 5.9 1.03 180
1-Melm b
6.8 1.76 180
a
This work. 1-Memylimidazole.
b

values of other Co(II) porphyrins. Porphyrin 48e has a similar binding constant for the first

binding of Py to those of 34c and 12h (see p.62 for the structures) and the value for 48e is larger

than that of 43. Thus, the result proves the electron-deficiency of the P-tetrakis(trifluoromethyl)-

OTWO-tetraphenylporphyrin ligand. The increment from the log for Py to that for Im of 48e, 43,

and 14h correlates with basicity of the ligands (pJQ values; Py: 5.22, Im: 6.65, and l-Melm:

7.06)158 hut the increase for 48e seems to be large compared to those for 43 and 14h. A

rationale for this phenomenon is that the smaller axial base (Im) is preferable for binding to

sterically hindered 48e.

6. Summary

P-Trifluoromethylporphyrins H TPP(CF )
2 3 3 (
4 7a)
, H TPP(CF )
2 3 4 (
4 8a)
,

H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 showed bacteriocHorin-like UV-visible spectra that suggest fixed

187t-electron pathways of these porphyrins (section B./.). The H N M R experiments using J

47a
 183

suggested that the porphyrin preferably takes the fixed 187t-electron pathway (section B.2). The

analysis of the H O M O - L U M O gaps of P-ttifluoromethylporphyrins obtained by cyclic

voltammetry also suggested that the tautomerism of the two electronic pathways of

/^jtf-tettaphenylporphyrin is shifted into one, like that of bacteriochlorin, due to the strong

electron-withdrawing effect of the —CF groups (section B.J).

3

The steric effect of the —CF groups was shown by the analysis of an X-ray crystal
3

structure of Zn(TPP(CF ) ) (48b) 3 4 (section B.4). The estimated van der Waals radius of - C F 3

from the crystallographic data is 2.7 A and the steric interaction between the meso phenyl groups

and the bulky —CF groups seems to be the driving force of a severe saddle distortion of the
3

macrocycle. The steric effect of the —CF groups in the P-tetealris(tofluoromediyl)porphyrin

3

ligand possibly correlates with the large red-shifts and broadening of the UV-visible absorption

bands, the unusual ' H N M R chemical shift for the pyrrolic P-protons, the non-linear increase of

the first oxidation potentials, and the slow base binding to the Co(II) complex.

Comparison of the reduction potentials, the pK value for the first deprotonation of the
a

N H protons, and the binding constant of Py and l m to Co(TPP(CF ) ) (48e) 3 4 with those of other

electron-deficient porphyrin systems proved that the P-tettalds(tjifluoromethyl)porphyrin ligand

is electron-deficient. The Fe(II/III) reduction potentials of Fe(TPP(CF ) )Cl (481)

3 4 and

Fe(TPP(CF ) (CF CF )Cl (52c)

3 3 2 3 were tuned in the ideal range for an oxidation catalyst; between

those of the second and the third generation porphyrin catalysts such as Fe(TPFPP)Cl (4d) and

Fe(TPFPPBr )Cl (8d).

8 Thus, the catalytic activities of 48f and 52c were investigated in order to

assess the usefulness of these complexes as oxidation catalysts.

 184

C. Cat
a l
y t
i
coxi
d at
i
o n of c
yco
lhe
xane and c
yco
lhe
xene

As reviewed in the first chapter, some electron-deficiency is necessary to improve the

catalytic activity and the robustness of metalloporphyrins. In order to investigate the usefulness

of the Fe(III) complexes of P-oifluoromethyl-OTMo-tetj:aphenylporphyrins Fe(TPP(CF ) )Cl3 4 (481)

and Fe(TPP(CF3)3(CF CF )Cl (52c)

2 3 as oxidation catalysts, hydroxylation of cyclohexane and

epoxidation of cyclohexene in C H C 1 2 2 was examined. As discussed briefly in Chapter I,

section A . Z d , detailed reaction conditions for catalytic oxidation in the studies of porphyrin

catalysts are diverse. Although we have to keep this point in mind, the performance of 48f and

52c was compared with that of one of the best porphyrin catalysts F e ^ D C P P C k j C l (10d)226

(third generation porphyrin catalyst) under the same reaction conditions.

In a catalytic oxidation of cyclohexane, to a C H C 1 solution containing 1 eq. of the

2 2

porphyrin catalyst and 5,000 eq. of cyclohexane, 200 eq. of PhIO were added during the first 1 h.

The reaction was performed in a vial at 24 °C for 4 h. The solutions of 48f and 52c are green but

both solutions turned orange instantiy when the first 50 eq. of PhIO was added and the orange

color gradually faded away during the reaction. The solution of 45e was greenish yellow at the

beginning of the reaction and it was bleached gradually too. The solution containing O
ld was

green and the color was almost maintained during the reaction. After the reaction, the liquid

phase of the reaction mixture was analyzed by gas chromatography. The results are summarized

in Table 2-16. Since the amount of substrate used is a large excess, normally the yield of the

product is given based on consumed oxidant; (peak area of cyclohexanoi)/(peak area of

Phi) x 100 is reported in Table 2-16.

 185

Tabl
e 2-16. Oxidation of cyclohexane and cyclohexene using Fe(III) porphyrins and
iodosylbenzene in C H C l . 2 2
a

. cyclohexanol cyclohexene oxide

y S t
Yield (%) b
turnover 1
Yield (%) b
turnover'
Fe(TPP(CF ) )Cl (481)
3 4 7 5 62 77
Fe(TPP(CF ) (CF CF ))Cl (52c)
3 3 2 3 9 6 61 61
Fe(TPPBr )Cl (45e)
4 5 4 68 82
Fe(TDCPPCl )Cl (O
l d) 8 44 86 89 109
a
Reaction conditions: CH C1 = 500 pL, catalyst = 1x10^ mmol,
2 2

cyclohexane = 5 x 10 mmol, cyclohexene = 1 mmol, PhIO = 2 x 10 ~ mmol. For

_ 1 2

hydroxylation; temp. = 24 °C, t = 4 h. For epoxidation; temp. = 30 °C, t = 2 h.

b
Based on PhIO consumed . Product (mmol)/catalyst (mmol). c

Although we cannot direcdy compare these data with the literature values such as those

shown in Chapter I, there was a clear difference between the yields with

p-trifluoromethylporphyrins Fe(TPP(CF ) )Cl (48f) 3 4 and Fe(TPP(CF ) (CF CF ))Cl (52c)

3 3 2 3 and the

third generation catalyst, Fe(TDCPPCl )Cl (

l
O d)
. Fe(III) porphyrins 48f and 52c are not good
8

oxidation catalysts at least under these conditions. The Fe(III) complex 45e was also found to be

ineffective for hydroxylation of cyclohexane. Bleaching of the solutions containing 45e, 48f, and

52c implies that these porphyrins may be decomposing during the reaction.

Epoxidation of cyclohexene was performed under the same conditions except for the

amount of the substrate. The yields of the epoxide from cyclohexene were much higher than

those for hydroxylation but the result shows that catalysts 48f and 52c are not as effective as

P-halogenated porphyrins. The solutions of 48f and 52c were not completely bleached during

the reactions but the color of the porphyrins faded away gradually.

Since a supply of 48f and 52c was not enough, thorough examination of hydroxylation and

epoxidation could not be performed. However, the preliminary tests regarding catalytic oxidation
 186

showed the instability and the ineffectiveness of 48f and 52c compared to one of the best

porphyrin catalysts lOd. Potential reasons for these results are:

The first oxidation potentials (ring oxidation) of 48f and 52c are about the same as that

of Fe(TPP)Cl (2d) (see Table 2-12). Oxidation of 48f and 52c is as easy as that of 2d.

The macrocycles are destabilized by severe distortion caused by the steric or the

electronic interaction between the peripheral substituents. Thus, the electron-

withdrawing effect of - C F groups does not contribute to improve robustness of the

3

macrocycle.

Although Fe(III) porphyrins 48f and 52c have four bulky perfluoroalkyl groups but

there are still (3-hydrogens and twenty phenyl-hydrogens. Thus, more protection of the

macrocycle may be required for robustness. As observed in the crystal structure of

Z n T P P (CF ) (
3 4
4 8b)
, meso-xphenyl rings are extremely tilted by the steric or the

electronic interactions with - C F groups. This may facilitate the formation of the
3

p,-oxo dimer. In fact, the u-oxo dimer (61) is easily formed from 48f (Scheme 2-8,

p.93).

Ligands 48 and 52 presumably take a bacteriochlorin-type electronic structure. The

macrocycles should be redox sensitive due to the small H O M O - L U M O gap; the low

first oxidation and the high first reduction potentials. Thus, this may trigger a

decomposition of the macrocycles.

As discussed in this Chapter, P-tafluoromethylporphyrins are electron-deficient and

introduction of the - C F groups on the pyrrolic P-positions of antipodal pyrroles leads to the
3
 187

unusual electronic properties and the structure of the macrocycle. However, this seems to be not

advantageous for an activity as oxidation catalysts.

 188

C H A P T E R III

Conclusions and Future Work

A . Conclusions

In these studies towards the synthesis of novel electron-deficient porphyrins, based on the

structure of ^jo-tetraphenylporphyrin, - C F 3 groups were introduced onto the pyrrolic

P-positions of the macrocycle using P-bromo-^wo-tetraphenylporphyrins and the agent in-situ

generated C F C u . Trifluoromethylation at the pyrrolic P-position of ^.ro-tettaphenylporphyrin

3

was difficult due to the steric bulkiness of the —CF group. Therefore, the maximum number of
3

—CF groups added to the porphyrin was four.

3

Partially introduced —CF groups at the antipodal pyrrolic P-positions not only made the
3

macrocycle electron-deficient but also directed the 187t-electron pathway of the porphyrin

macrocycle to take one similar to that of bacteriochlorin. The unique electronic structure of the

P-tofluoromethylporphyrins resulted in red-shifted bacteriochlorin-like UV-visible spectra. The

unique electronic pathway in the novel porphyrins was proved by the locked positions of N - H

protons determined by ' H N M R spectroscopy. The analysis of the redox potentials of

P-tofluoromethylporphyrins showed a progressive decrease of the H O M O - L U M O gap along

with the antipodal trifluoromethylation. This was also an indication of the bacteriochlorin-like

distorted 187t-electronic pathway. Redox potentials also enabled approximate comparison of the

electron-deficiency of P-trifluoromethylporphyrins with other electron-deficient porphyrin

systems. However, the comparison has to be done carefully because in the conclusion of this

work, the electronic structure of the novel p-teifluoromethylporphyrins is different and thereby
 189

the redox potentials may change. The electron-deficiency of p-tettalds(mfluoromethyl)porphyrin

was evaluated to be the same as the reported electron-deficient porphyrins such as P-octafluoro-

/wwo-tettaphenylporphyrtn (TPPFg) or P-teteacycano-/W£ro-teteaphenylporphyrin (TPP(CN) ) by 4

the determination of the pXa and the axial base binding constants to Co(II) porphyrin.

The - C F groups on the pyrrolic P-positions also exhibited a large impact on the structure
3

of the macrocycle as a result of steric interactions between - C F and - C F groups and between
3 3

-CF 3 and phenyl groups. The macrocycle of P-tetrakis (trifluoromethyl) -meso-

tetraphenylporphyrin is distorted into a saddle shape. The van der Waals radius of the - C F 3

group obtained from HyperChem and the X-ray crystal analysis is 2.7 —2.8 A, which is large

enough for steric interaction between the substituents to lead to such macrocycle distortion.

Fe(III) complexes of P-trifluoromethylporphyrins showed a well-tuned Fe(III/Il) redox

couple which was comparable to those of good porphyrin catalysts such as the second and the

third generation porphyrin catalysts. However, it was found that Fe(III) complexes of

P-tofluoromethylporphyrins were not superior catalysts to the third generation porphyrin catalyst

Fe(TDCPPCl )Cl in oxidation of cyclohexane and cyclohexene. Stability of the catalysts seems to
8

be the problem. The unique electronic structure of the P-trifluoromethylporphyrins could be

disadvantageous for a stable macrocycle system.

B. Fut
u r
ewo
rk

Studies of redox properties of the macrocycle in a series of porphyrins bearing strong

electron-withdrawing groups such as —CN or —NO have been reported37>161 but the detailed
z

electronic structures and spectroscopic properties have not been reported in the literature.
 190

Although redox properties of some series of P-brominated zwo-tettaphenylporphyrins have been

extensively studied by Kadish et « / , 1 6 2 - 1 6 4 a unique electronic structure of the macrocycle like

the system observed in this work has not emerged in the series of brominated porphyrins

probably because the —Br group is mildly electron-withdrawing. One way to continue these

investigations regarding the electronic structures of the macrocycle may be to extend the series

of P-trifluoromethyl-^j'o-tetophenylporphyrins. This would allow us to see the change in

spectroscopic and electrochemical data through which we could determine the electronic

structure ofthe macrocycle. However, the synthesis of highly P-trifluoromethylated porphyrins is

challenging and may not be productive because P-pyrrolic positions are not suitable for smooth

introduction of —CF groups. In addition, separation becomes more difficult as the number of
3

perfluoroalkyl moieties increases. Thus, the details of effects of extremely strong electron-

withdrawing substituents on the electronic structure of the macrocycle may be investigated by

P-cyano or p-nitroporphyrins. P-Nitration of a ^wo-tetraarylporphyrin is fully controllable by the

method recently devised by Palacio et affl and allows access to P-mono- to

P-octanitroporphyrins.

Although trifluoromethylation on the pyrrolic P-position of the macrocycle is difficult, a

different porphyrin system may be synthesized to achieve high-performance porphyrin catalysts.

A potential porphyrin candidate is shown in Scheme 3-1. The first measure Groves et al. took to

achieve some improvement from Fe(TPP)Cl (Figure 1 -8) was to introduce the steric bulk on the

periphery of the macrocycle and Fe(TMP)Cl (Figure 1-8) appeared.98 This porphyrin,

(Fe(TMP)Cl), is not likely to be a good catalyst for oxidations. The meso- and pyrrolic
 191

P-positions are protected by the bulky mesityl groups but methyl groups in the mesityl

groups are exposed to the exterior. These are problematic for robustness of the catalyst. If a

metal complex of w<?.ro-tetealds(2,6-dibromophenyl)porphyrin (65) and C F C u are used, T M P -

3

analogous OT^o-tettakis(2,6-bis(tofluorometiiyl)phenyl)porphyrin (66)(Scheme 3-1 (a)) may be

obtained. The synthesis of 66a was attempted by Lindsey et al. by condensation of pyrrole and

2,6-bis(tofluoromediyl)benzaldehyde67 but was unsuccessful, presumably due to the steric

hindrance of the two —CF groups on the benzaldehyde, preventing cyclization with pyrrole. In
3

the porphyrin, the o^o-positions of the meso-phenyl groups are not hindered and thus

introduction of the —CF groups there may not be as difficult as that of the pyrrolic p-positions.
3

A geometry optimized molecular structure of 66a by HyperChem (Scheme 3-1 (a) and (b)) shows

a planar macrocycle and four orthogonal meso-aryl groups to the macrocycle. The —CF groups 3

are more stable and bulkier than the — C H groups (Chapter I, section B.J.b). Thus, it is expected
3

that the —CF groups may protect the macrocycle effectively. The distance from the macrocycle
3

to the edge of the ortho-CP^ groups (Scheme 3-1 (c)) is approximately 5 A. This distance also

suggests that formation of the p-oxo dimer would be unlikely. Finally the meso-2,6-

bis(trifluoromethyl)phenyl groups are electron-withdrawing and they can keep the macrocycle

electron-deficient. One problem for this future work may lie in the synthesis of porphyrin 65,

which is a known compound synthesized by condensation of pyrrole and

2,6-dibromobenzaldehyde.67 However, 2,6-dibromobenzaldehyde is not manufactured right

now. Thus, we need to synthesize 2,6-dibromobenzaldehyde in order to obtain porphyrin 65.

Attempts towards the synthesis of P-octolds(ttifluoromethyl)-^j"o-arylporphyrins may not

be an appropriate direction for improvement of the catalytic activity of porphyrin catalysts. The
S
che
m e 3-1. wwo-Tettakis(2,6-bis(rjifluoromemyl)phenyl)porphyrin (66).
(a) A possible synthetic route for 66. (b) A computer m o d e l o f 66a.
(c) A side view o f the computer m o d e l . 1 8 9
 193

eight —CF groups on the pyrrolic p-positions promise a high electron-deficiency of the
3

macrocycle, but too much electronegativity may lead to stable Mn(II) or Fe(II) porphyrins, which

are inactive as monooxygenase systems, as shown by Grinstaff ^ « / . ( F e ( I I ) ( T P F P P B r ) ) 0 7

8
1
a n c j

BartoH eral ( M n ^ t T D C P P f N O ^ ) . 4 7
Therefore, super electron-deficiency is not an ultimate

solution for a perfect cyctochrome P-450 mimic.

The ultimate goal for P-450 model compounds may be to let metalloporphyrins utilize

molecular 0 2 (or air) as a source of oxidant to form the oxo Fe(IV) porphyrin 7t-cation radical,

the key intermediate in the P-450 catalytic cycle. ^ ^ As reviewed in Chapter I, two electrons
2 4

and two protons are required in order to form the intermediate from Fe(III) porphyrin and 0 2

and to reduce one of the oxygen atoms of 0 2 to water. Thus, mimicking the P-450 cycle with

only 0 2 and synthetic Fe(III) seems very difficult. However, the oxo Fe(TV) porphyrin 7i-cation

radical can be also formed via the shunt path (see Figure 1-5) using an oxygen atom transfer

reagent. Although there are variety of " O " transfer reagents such as N a O C l , PhIO, peroxides,

and peroxy acids, the use of these reagents generates by-products (NaCl, Phi, etc.). A n exception

is hydrogen peroxide. Although hydrogen peroxide is more costiy than molecular 0 , it is a 2

competitive source of oxygen atoms with molecular 0 . since it is a clean and environmentally
2

friendly o x i d a n t . 227
A n ideal reaction of Fe(III) porphyrin and hydrogen peroxide for catalytic

oxidations is shown in Scheme 3-2(a) (Path A), where heterolytic O - O bond cleavage of

Fe(III)-0-0-H occurs to form the oxo Fe(IV) porphyrin 7T-cation radical. For this type of

cleavage, polarization of the O - O bond is necessary.53 As shown in Scheme 3-2(b), the - C F 3

groups on the ortho-positions of the meso-aryl groups might help polarization of the O - O bond
 194

via the hydrogen bonding. Formation of p-peroxoclimer (Scheme 3-2(a), Path B) should be ruled

out due to the bulky —CF groups.

3

The ortho-CP\ groups might play the following important roles in catalytic oxidations;

(1) protection of the macrocycle by their steric and electron-withdrawing effects, (2) formation

oxo Fe(TV) porphyrin Tt-cation radical by the use of H O via an intramolecular interaction, and
2 z

(3)activation of the active intermediate by electron-withdrawing effects. Therefore, investigation

of metal (such as Fe(III) or Mn(III)) complexes of porphyrin 66 may provide new insights for

the development of cyctochrome P-450 model compounds.

M + H

X O
H,0
2^2 Path .4
(a) Fe(lll) Fe(lll) Fe(IV)
•H,0

Path B PFe(lll)

porphyrin
dianion O
x = anion (Cl", OH", etc.)
2x Fe(IV)
PFe(lll):

(b)
-FUO \ _

Scheme 3-2. Formation of oxo Fe(IV) porphyrin 7t-cation radical from Fe(III)
porphyrin and hydrogen peroxide, (a) Reaction pathways, (b) Mode of activation of
the O - O bond.
 195

C H A P T E R IV

Experimental

A . Chemicals

All chemicals for synthesis were purchased from Sigma-Aldrich fine chemicals, Across

Chemicals, or Fisher Scientific. If necessary, chemicals were purified by published

procedures. ^ Deuterated solvents for N M R measurements were purchased from Cambridge

22

Isotope Laboratories or Aldrich. Chlorinated solvents were filtered using N-alurnina (activity I)

to remove trace acid (HC1 or DC1). Column chromatography was performed using 70 - 230 or

230 - 400 mesh silica gel (Merck). Analytical thin-layer chromatography was performed using

pre-coated silica gel aluminum plates which contains a fluorescent indicator (GF 254 Merck).

B . Instrumentation

UV-visible spectra were recorded on a Varian Cary 50 scan UV-visible spectrophotometer

or a Hewlett-Packard 8452A diode array spectrophotometer. N M R spectra were recorded on

Bruker AC-200, WH-400, or Avance 300 spectrometers. Cyclic voltammetry measurements were

performed on a Pine Instrument Company bipotentiostat model A F C B P 1 and Pine Chem

Sweep Voltammetry software for Windows v. 2.00. The cyclic voltammetric experiments were

performed using an electrochemical cell as shown in Figure 4 - 1 . 2 2 9

X-ray crystallographic data

were collected on a Rigaku/ADSC C C D . A Hewlett-Packard G C HP-17 was used to detect

oxidation products. This G C utilizes a phenyl methyl silicone (50 % crosslinked, 25 m x 0.32 m m

x 0.26 um (length x tubing inner diameter x film thickness)) capillary column, and a flame

ionization detector, and helium was used as a carrier gas.

 90°

Fi
g ur
e 4-1. Electrochemical cell and electrodes (a. Pt working electrode,
b. A g reference electrode, c. Pt counter electrode).
 197

C . Procedures

Cyclic voltammetry. C H C 1 and P h C N were distilled and degassed by three cycles of the
2 2

freeze-pump-thaw method and dried over activated molecular sieves 4A. A sample solution for a

measurement was prepared by the following procedure. A r was introduced from gas inlet E (see

Figure 4-1 for designations A - E and a - c). The electrochemical cell was dried using a heat gun.

Electrodes a, b, C were also dried using a heat gun and placed in A, B, C of the cell, respectively,

so that the electrodes did not contact each other and were then cooled under a slow A r stream.

For a typical measurement, porphyrin typically (0.015 - 0.03 mmol), and T B A P F (0.3 mmol)
6

were weighed and transferred to the cell through D. Dry solvent (3 mL) was then introduced

into the cell through D. The solution was bubbled with A r for a few minutes, and then D was

closed with a glass stopper. The connections at A, B, C, and D were secured with parafilm. A n

A r balloon was put on E and the stopcock was then opened. Porphyrin was dissolved completely

using a sonicator. The cell was connected to the potentiostat and voltammograms were recorded

without stirring the solution. In order to standardize the potentials, ferrocene (0.005 mmol) was

added to the solution from D. Voltammograms were recorded again under the same conditions.

Addition of ferrocene did not affect the redox potentials of porphyrins.

Spectrophotometric titrations. (Titration of H TPP(CF )

2 3 4 (48a) with DBU and Et^SS).

Titrations were performed by the following procedure. The concentration of 48a was set to

9.66 x 10 -3
m M while varying the concentration of D B U within the range of 0-2.1 x 10 2
M.

The color change was noted immediately upon addition of D B U to the solution containing the

porphyrin. Solutions were made up in H P L C grade C H C 1 and the UV-visible spectrum of each
2 2

batch was recorded. The same procedure was followed for the spectrophotometric titration

using E t N .
3
 198

The pK for the first deprotonation of H T P P ( C F ) (48a)

a 2 3 4 was determined by the following

analysis. According to the Lambert-Beer law, ^0 2

m e following equations, (4.1) and (4.2) can be

written with the assumption that only the porphyrin species contributes to the absorbance at the

-^463 —
£463'Q-I2P ^~'~ ^463'CHP-'^ -
(4-1)

-A-513 — 5lVQ-I2P'^~'~
£
( - )4 2

selected wavelengths, where A 4 6 3 and A 5 1 3 are the total absorbances, s ^ , S ™ , s " , and S™~are
3 3
2
3

the extinction coefficients of the free-base porphyrin (H P; P ~ = dianion of 48a)

2
2
and the

porphyrin mono anion (HP ), C -

H 2 P and C,. ,- are the concentrations of H P and H P " at 463 and
n 2

513 nm, respectively, and / is the cell path length, 1 cm. Given the molar extinction coefficients

and absorbances, the concentrations of the free-base and the mono anion are determined by the

following equations (4.3) and (4.4).

HP- * HP- A
prj -|-yi
&
463 -"513
J I J 513
J 1J -"-463
tuj
&
J /A

|H 1 J -
2 H 2 p H p_ H p 2 H p. (4.3)
FC
513 463 463 513FC FC FC

E 2 A H P
-E 2 A H P

V nl
J H
2 P
P H P
- oB 2H P
p H P
" V*' V
^463 513 "" 513 463
P B B

Also, the relationships between concentrations of protonated D B U ( D B U H ) , H P , initial +

D B U , and D B U at each titration point are written as (4.5) and (4.6).

P B U H ] = [HP"! (4.5)+

PBU] = pBU] - pBUH ] 0

+
(4.6)
 199

The equilibrium constants K H2P and i<C DBU for deprotonation of H P and D B U H
2
+
are

written as (4.7) and (4.8).

H P^HP + H
2
+
K H2P = ]
(4.7)

DBUH -DBU + H + +
KDBU = pBUPT] 1
(-)
4 8

The equilibrium constant for the H P - D B U reaction can be rearranged as (4.9).

2

H P + D B U ^ HP'+ D B U H
2
+
K= ^ ^ B U ] 1
^

= W*DBU (4-9')

Logarithm of both sides of (4.9) gives:

|H,P1 PBUH ] +

^S = P I C + L O G
W (4
- 9)

Analysis of titration data using (4.3) - (4.6) and (4.9") should give a straight line with the

slope of 1 and the intercept of pK.

PK=pK -pK =ApKH2P Dm t (4.10)

(Spectrophotometric titration of48e with pyridine and imidazole). C H C 1 and pyridine were distilled 2 2

and degassed by three freeze-pump-thaw cycles, and dried over activated molecular sieves (4A).
 200

A C H C 1 solution of Co(rPP(CF ) ) (48e)

2 2 3 4 (8.60 x 10" mM) in a 1 cm path length cuvette was
3

titrated with a pyridine solution (0 - 3.4 x 10 -1

M) prepared in CH C1 . Titration was performed
2 2

in a N glove bag. After each injection of the titer, the cuvette was tighdy capped with a Teflon
2

top to take out to UV-visible spectral measurements. In order to make sure that the reaction

reached equikbrium, the UV-visible spectrum was monitored for 20 min after each titration. For

higher concentrations of pyridine, neat pyridine was used. The concentrations of the species in

the cuvette were corrected with the volume of the added titer. The same procedure was followed

for the titration using imidazole. For higher concentrations of imidazole, solid was direcdy added

to the cuvette. The binding constant was determined according to the following analysis. ^ The 22

binding constant is written as (4.11).

K [CoPB]
CoP + B ^ C o P B , K-^pj.pjj (4.11)

CoP: four-coordinate Co(TPP(CF3)4) (48e), B: pyridine or

imidazole, CoPB: five-coordinate Co(II) porphyrin pyridine
complex.

The mass balance regarding Co complexes is written as (4.12).

[CoP] + [CoPB] = [CoP] 0 (4.12)

[CoP], [CoPB], and [CoP]o: concentrations of CoP and C o P B

during the titration and the initial concentration of CoP,
respectively.

From (4.11) and (4.12), (4.13) is obtained.

[CoP] 0

K
P] + 1 =
[CoP] ( - )
4 13

According to the Lambert-Beer law,

 201

A = e [ C o P ] , / = l c m (4.14)
0 0

A = s'[CoPB] = £'[CoP]
F f 0 (4.15)

A = s [CoP] + e'[CoP-B] (4.16)

Ao, Af, and A: the absorbances initially and finally, and during the
titration, respectively, at the monitored wavelength. 8 and £': the
extinction coefficients of CoP and CoPB at the wavelength.
[CoPBJf: the final concentration of CoPB.

From (4.14), (4.15), and (4.16), (4.17) is obtained.

[CoP] A-A f ^ A / )

Substitution of (4.13) into (4.17), rearranging and taking the log of the resultant equation

gives (4.18).

L 0 G
(A^) = 1
° ^ 8 + L 0 G [ B ] ( 4
- 1 8 )

The concentration of B is obtained from (4.19).

[B] = [B] - [CoPB] = [B] - ([CoP] - [CoP]) = [B] - [ C o P ] - ^

tot tot 0 tot 0 (4.19)

[B] ot:
t the total concentration of the base.

VA'
Thus, the plot of log [B] vs. log ^ ^ J should give a straight line with the slope equal to 1.

The y intercept is the log K value.

 202

Gas c
h r
o ma
togr
aphy
. For the analysis of cyclohexane oxidation, a typical temperature

program was 40 °C (3 min) -» 20 ° C / m i n -» 220 °C (10 min). Injection temp, and F I D temp.:

220 °C. Retention times for CH C1 , cyclohexane, cyclohexanol, and iodobenzene were 1.02,
2 2

1.23, 5.36, and 7.40 min, respectively. For the analysis of cyclohexene oxidation, the program

was 25 °C (3 min) — 20 ° C / m i n — 220 °C(10min). Injection temp.: 180 °C. F I D temp.: 220 °C.

Retention times for CH C1 , cyclohexene, cyclohexene oxide, and iodobenzene were 1.25, 1.80,
2 2

6.48, and 7.48 min, respectively.

D. Pr
e par
a t
i
o n of mat
e r
i
a l
s

5
1
,01
,5
2
,0-
T e
tr
aphe
n y
p
lor
p hy
rn
i (
H TPP) (2a). 2 The porphyrin was synthesized by a

published procedure. 64
UV-vis (Ct^CL): A, max (nm) 418 (Soret), 514, 549, 590, 646.

'H N M R (CDC1 ): 8 -2.76 (s, 2 H , N H ) , 7.75 (m, 12H, phenylp- and m-H), 8.22 (m, 8H, phenyl
3

o-H), 8.86 (s, 8H, pyrr-P-H); ( Q D ^ : -2.13 (s, 2 H , N H ) , 7.44 (m, 12H, phenyl p- and m-H),

8.10 (m, 8H, phenyl o-H), 8.91 (s, 8H, pyrr-P-H). The spectroscopic characteristics of this

compound compare well to those reported in the literature. 64

5,
1 0,
1 5,
2 0-
T et
raphenyl
p or
p hyr
i
n at
o z
i
n c(
I
) (
Z n(
T PP)
) (2b). The porphyrin was

synthesized by a published procedure. 68

UV-vis ( C H ^ L ) : A, max (nm) 419 (Soret), 548, 582.

*H N M R (CDCI3): 5 7.73 (m, 12H, phenyl p- and m-H), 8.08 (m, 8H, phenyl o-H), 8.90 (s, 8H,

pyrr-P-H). The spectroscopic characteristics of this compound compare well to those reported in

the literature.- "3 6

Chl
o r
o (
5 ,
1 0,
1 5,
2 0-
t
e t
raphenyl
p or
p hyr
i
n at
o )
i
ron(
I
)(Fe(
T PP)
C l
) (2d). Metallation

using FeCl and oxidation to the Fe(III) complex were achieved by a published procedure.
2
69
 203

' H N M R (CDCL): 8 5.11 (s, 4 H , phenyl o-H), 6.39 (s, 4H, phenyl p-H), 7.98 (s, 4 H , phenyl o-H),

12.17 (s, 4 H , phenyl m-H), 13.32 (s, 4 H , phenyl m-H), 79.46 (s, 8H, pyrr-p-H). The spectroscopic

characteristics of this compound compare well to those reported in the literature. ! 23

5,
1 0,
1 5,
2 0-
T et
raki
s (
p er
f
l
u or
o phenyl
)
p or
p hyr
i
n (
H TPFPP) (4a). 2 The porphyrin was

synthesized by a published procedure . UV-vis (CH OJ:

232
2 Xmxi (nm) 410 (Soret), 505, 535, 582,

635. ' H N M R (CDC1 ): 8 -2.50 (s, 2 H , N H ) , 8.80 (s, 8H, pyrr-p-H).

3
1 9
F N M R (CDC1 ),: 5 (vs. 3

CFCI3) -137.0 (d, 2F, aryl o-F), -151.7 (t, IF, arylp-¥), -161.8 (m, 2F, aryl m-F). The spectroscopic

characteristics of this compound compare well to those reported in the literature. 233

5,
1 0,
1 5,
2 0-
T et
raki
s (
p er
fl
u or
o phenyl
)
p or
p hyr
i
n at
o z
inc(
I) (
I Z n(
T PFPP)
) (4b). Zn(II)

was inserted into 4

a by a published procedure using Z n ( O A c ) - 2 H 0 . UV-vis (CF^CL):
2 2
6 8

\nax (nm) 414 (Soret), 544. ' H N M R (CDC1 ): 5 9.17 (s, 8H, pyrr-p-H).
3
, 9
F N M R (CDC1 ): 8 (vs. 3

CFC1 ) -138.5 (d, 2F, aryl o-F), -154.8 (t, IF, arylp-F), -163.7 (m, 2F, aryl m-F). The spectroscopic
3

characteristics of this compound compare well to those reported in the literature.78> 4 23

7
8
,1
,7
1
,8-
T e
tt
abr
o mo-
51
,0
1
,52
,0
-t
etr
aphe
n y
p
lor
p hy
rn
i (HTPPBr
)(
245a)
. The 4

porphyrin was synthesized by published proceduresl85,186 except for the purification process.

Analytically pure porphyrin was obtained by the following procedure. Crude product (100 mg)

was dissolved completely in hot chloroform (30 mL) and silica gel (30 m L — 15 g, 70 - 230

mesh) was mixed into the solution. The solvent was removed at room temperature in a fume

hood. The color of the porphyrin-adsorbed silica gel was brown. The brown silica gel was loaded

on top of silica gel (2 x 20 cm) wet with benzene/hexane 50:50 (v/v) and the impurities (mainly

H T P P B r ) were eluted with the solvent of the same composition. The main brown fraction was
2 3
 204

coUected with 100 % benzene. UV-vis ( C F L A ) : ^(nm) 436 (Soret), 534, 616, 686.

l
n N M R (CDC1 ): 5 -2.83 (s, 2H, N H ) , 7.78 (m, 12H, phenyl p- and m-H), 8.18 (m, 8H, phenyl
3

o-H), 8.68 (d, 4 H , pyrr-p-H); ( Q D ^ : 8 -2.69 (s, 2H, N H ) , 7.50 (m, 12H, phenyl p- and m-H),

8.04 (m, 8H, phenyl o-H), 8.54 (d, 4 H , pyrr-p-H); ( C F C 0 D ) : 8 8.37 (m, 12H, phenyl p- and
3 2

m-H), 8.68 (m, 4 H , phenyl. o-H), 8.92 (m, 4H, phenyl o-H), 8.75 (s, 4H, pyrr-p-H). The

spectroscopic characteristics of this compound compare well to those reported in the

Uterature. 185,186

2,3,12,13-Tetrabromo-5,10,15,20-tetraphenylporphyrinatozinc(II)

(Zn(TPPBr ))(45b). 4 Zn(II) was inserted into 45a by a published procedure using

Zn(OAc) -2H 0. 2 2
68
L R - M S (EI, 300 °C): M ( m / z ) = 993 , calcd. for C H B r N B r : 993.6888.
+
44 24 4 4

UV-vis (CH.CL): X m a x (nm) 430 (Soret), 560, 598. H N M R (DMSO-d,): 8 8.61 (s, 4 H , pyrr-P-H),
]

8.02 (m, 8H, phenyl-o-H), 7.80 (m, 12H, phenyl-/? and m-H). The spectroscopic characteristics of

this compound compare well to those reported in the literature. -^ 2

2,3,12,13-Tetrabromo-5,10,15,20-tetraphenylporphyrinatocopper(II)

(Cu(TPPBr ))(45c). 4 Cu(II) was inserted into 45a by a published procedure using

Cu(OAc) -H 0. 2 2
6 8
L R - M S (EI, 300 °C): M ( m / z ) = 991 , calcd. for C ^ H ^ B r . N . C u : 991.8828.
+

UV-vis (CHjCL): A, max (nm) 426 (Soret), 553, 586. The spectroscopic characteristics of this

compound compare well to those reported in the literature. - ^ 2 3

2,3,12,13-Tetrabromo-5,10,15,20-tetraphenylporphyrinatonickel(II)

( N i ( T P P B r ) ) ( 4 5 d ) . Ni(Ii) was inserted into 45a by a published procedure using N i C l .

4 2
6 8
LR-

MS (EI, 300 °C): M ( m / z ) = +

987, calcd. for C ^ H ^ B r . N . N i : 987.0528. UV-vis (CH.CL):
 205

Xmax (nm) 428 (Soret), 544, 538. The spectroscopic characteristics of this compound compare

well to those reported in the literature.235

Chloro(2,3,12,13-Tetrabfomo-5,10,15,20-tetraphenylpotphyrinato)iron(III)

( F e ( T P P B r ) C l ) (45e). Insertion of Fe(II) and formation and purification of this Fe(IIi)

4

complex were achieved by published procedures^,! 90 UV-vis ( C H j C y : (nm) 433 (Soret),

520, 591, 714. ' H N M R (CDC1 ): 5 4.77 (s, 4 H , phenyl o-H) 6.59 (s, 4 H , phenylp-H), 7.41 (s, 4 H ,
3

phenyl o-H), 12.46 (s, 4 H , phenyl m-H), 13.19 (s, 4 H , phenyl m-H), 79.49 (s, 4 H , pyrr43-H). The

spectroscopic characteristics of this compound compare well to those reported in the

literature.191

2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tettaphenylporphyrinatocopper(II)

( C u ( T P P B t ) ) (7c). The porphyrin was synthesized by a published procedure.^. L R - M S (EI,

8

300 °C): M ( m / z ) = 1307, calcd. for C ^ H ^ B r ^ C u : 1307.4908. UV-vis (CPECy:

+
^(nm)

365, 448 (sh), 466 (Soret), 581, 625. The spectroscopic characteristics of this compound compare

well to those reported in the literature.75

S o d i u m trifluoromethylacetate (CF C0 Na).

3 2 N a O H aqueous solution (0.75 M) was

slowly added to a solution of trifluoroacetic acid, 99 % (5.76 m L (75 mmol) in 100 m L H 0 ) . 2

This solution was stirred and the p H monitored. As the p H of the solution approached 5 - 6 , the

N a O H solution to be added was diluted to about 0.1 M and further added to the solution of p H

5 - 6 . Near p H 7 more diluted N a O H solution was used to adjust the p H at 7.0. The neutralized

solution was transferred to a 500-mL round-bottomed flask and most of the water was removed
 206

by a rotary evaporator. A hygroscopic white solid was obtained. The wet solid was transferred to

a vial and dried under in vacuo at 100 °C overnight. The product was kept in a desiccator.

Tr
f
i
u
lor
o me
thy
c
ladmu
im (
C F
C dBr + (CF)Cd)). This reagent was synthesized by the
3 32

published procedure. 139 Trifluoromethylcadmium reagent was obtained as ca. 1 M solution of

trifluoromethyl anion in D M F . 1 9
F N M R (DMSO-d,): 5 (vs. CFCL) -33.2 (CF CdBr), and -33.9. 3

These chemical shifts agree with the reported values. 39 ((CF ) Cd), each of which was 1
3 2

accompanied by the satellite peaks by i n

C d and 113
C d . J ( C d - F ) : C F C d B r , 370.9; (CF ) Cd,
,,3 19
3 3 2

423.7 Hz. J ( C d - F ) : CF CdBr, 355.9; (CF ) Cd, 404.8 Hz. The concentration of CF " was
m ,9
3 3 2 3

determined by the ratio of the peak integration to the internal reference, 3-fluorotoluene. The

spectroscopic characteristics of this compound compare well to those reported in the

literature. 139

P-
T r
i
f
luor
o met
h yl
-
w eso-
t
e t
raphenyl
p or
p hyr
i
n s. (Pyrolysis of CFjCO^a) A one-neck

100 m L round-bottom flask equipped with a N 2 inlet was charged with C F C 0 N a (2.70 g,3 2

19.8 mmol), C u l (1.52 g, 8.00 mmol), Zn(TPPBr ) (45b) 4 (0.500 g, 0.503 mmol), dry D M F

(15 mL) and toluene (5.5 mL). The flask was equipped with a distillation apparutus and toluene

was removed during the first one hour at 120 °C under a N stream. The reaction mixture was 2

then heated up to 150 °C. C0 (g) generation started at about 145 °C. The mixture was allowed
2

to cool after 1 h and D M F was removed by a rotary evaporator. C H C 1 (50 mL) was added to 2 2

the green product and the resulting solution was passed through a short silica gel column to

remove the inorganic salts. The volume of CH Cl was reduced to about 10 mL, T F A (4 mL) was
2 2

added and the mixture was refluxed for 1 h. The brown solution was diluted to ~100 m L with

C H C 1 and washed with the same amount of water 3 times. Silica gel T L C of the free-base
2 2
 207

porphyrin mixture showed three distinctive spots for H T P P ( C F ) 2 3 2 (

4 6a)
, H TPP(CF ) (
2 4 7a)
, 3 3

and H T P P ( C F ) (48a)
2 3 4 (Rf = 0.58, 0.47, and 0.09, respectively. CH Cl :hexane=5:5 (v/v)). In
2 2

addition to these three spots, some less intensive spots were observed between 47a and 48a.

Compound 46a, 47a, and 48a were separated by silica gel column, by changing the composition

of solvent mixture gradually (CH Cl /hexane = 30/70 -» 50/50 -» 70/30 — benzene (100)).
2 2

Since the solubility of 48a was low in this solvent system, the mixture of 46a, 47a, and 48a was

pre-adsorbed on a minimal amount of silica gel before column chromatography. The solvents

were removed from each fraction to yield 46a (60 mg, 16%), 47a (120 mg, 29%), and 48a

(11 mg.
2 .
5 %)
.

(Metathesis of trifluoromethylcadmium) A typical example of this reactions is shown below. As

shown in chapter II, reaction temperatures and times were varied. Trifluoromethylcadmium

reagent (14 mL, ca.l M) and dry H M P A (14 mL) were transferred to a two-neck 100 m L round-

bottom flask and the mixture was cooled down to 0 °C and stirred for 3 min under N . T o this 2

brown solution CuBr (1 g, 7 mmol) was added and the mixture was stirred until the CuBr was

dissolved at room temperature. Zn(TPPBr ) (45b) 4 (0.5 g, 0.5 mmol) was then added and the

mixture was heated at 90 °C for 7 h under N . After the mixture was cooled to room
2

temperature, D M F was removed by a rotary evaporator at 100 °C and small amount of H M P A

was removed at 2 - 3 mmHg at 100 °C. HMPA could not be removed completely.

Trifluoromethylated porphyrins were extracted with petroleum ether (35-60) until the green

color of the petroleum ether became weak. The resultant residue which remained after the

petroleum-ether extraction was dissolved in minimum amount of C H C 1 and approximately the

2 2

same volume of silica gel (230 - 400 mesh) was added to adsorb the impurities and porphyrin

products. After drying the pre-adsorbed silica gel for several hours at room temperature, it was
 208

packed in a short column without additional silica gel and washed with benzene. Only the green

porphyrin products were extracted and the brown impurities remained on the silica gel phase.

The green benzene solution was then combined with the petroleum-ether extracts. Volatile

solvents were removed in vacuo, H M P A * was distilled off at 100 - 110 °C at 2 - 3 mmHg. The

product was dissolved in C H C 1 and filtered. C H C 1 (50 mL) and T F A (10 mL) were added to
2 2 2 2

the green solid and the mixture was refluxed over a steam bath for 30 min until the color became

dark orange. The mixture was diluted with CH C1 , washed with 4 M HC1, distilled water, and
2 2

10 % aq. N a H C 0 . CH C1 , was removed and the free-base mixture was dissolved in a miriimum
3 2 2

amount of benzene and adsorbed on silica gel (230 - 400 mesh, same volume as the benzene

solution). After drying at room temperature in the fume hood, the pre-adsorbed silica gel was

loaded on top of a wet silica gel bed prepared using 5 x volume to the amount used for pre-

adsorption and chromatographed with CH Cl /hexane 2 2 (30/70 (v/v) -»• 50/50) to isolate

H T P P ( C F ) (46a)
2 3 2 (34 mg, 9 %) and H T P P ( C F ) (47a)
2 3 3 (86 mg, 21 %). The remaining

porphyrins on the column were washed with benzene/acetone (90/10 (v/v)). The solvents were

removed and the porphyrins were dissolved in benzene and pre-adsorbed on a minimum

amount of silica gel (230 — 400 mesh). Pre-absorbed silica gel was place on top of a wet silica gel

bed prepared using 7 — 8 x volume of silica gel to the amount used for pre-adsorption and flush-

chromatographed with benzene/cyclohexane/acetone (20/80/2 (v/v/v) ->• 50/50/2 -*

90/0/10)). Yield; H T P P ( C F ) (48a)

2 3 4 (140 mg, 38 %), H T P P ( C F ) ( C F C F ) (52a)
2 3 3 2 3 (47 mg, 10%),

54a (trace).

* Caution ! H M P A is a carcinogen and highly toxic. Distillation must be performed with an apparatus equipped with double traps
in a fume hood.
 209

46a showed a single mass corresponding to P-bis(trifluoromethyl)-w^o-

tetraphenylporphyrin by mass spectroscopy. However, ' H N M R of 46a did not show a clear

spectrum corresponding to a specific regioisomer. Two very close bands that could not be

separated were recognized by T L C analysis of 46a on a silica gel plate using CH Cl /hexane 2 2

(10/90(v/v)) as a solvent. 1 9
F N M R of 46a showed two singlets whose chemical shifts were very

close. Thus, 46a could be a mixture of regioisomers, 46a' and 46a" (p.71). The mixture of the

regioisomers was used throughout the experiments (e.g. UV-vis spectroscopy and cyclic

voltammetry).

As for 47a, the structure of the porphyrin was confirmed by the following analysis. There

are seven possible regioisomers for p-tris(trifluoromemyl)-^j'o-tetraphenylporphyrin in terms of

the occupancy of the eight pyrrolic P-positions by three - C F groups (Figure 4-2). H N M R of
3
!

47a (Figure 2-15, p.120) showed one singlet and four doublets (AB quartet) for the five pyrrolic

P-protons. Four structures, 47-3, 47-4, 47-5, and 47-6 are ruled out because the ' H N M R spectra

of these compounds would have to consist of three singlets and two doublets. 47-0, 47-1 and

47-2 are expected to show one singlet and four doublets. However, for 47-1 and 47-2, in order to

satisfy the result of the H C O S Y spectrum (Figure 2-16, p.121), the positions of the N - H
!

protons must be as shown in 47-1' and 47-2' (box in Figure 4-2). It is known that such tautomers

are not stable due to penetration of each proton into the van der Waals sphere of the other and a

N - H tautomer with two inner protons on transannular nitrogens is the most probable. 141 Thus,

47-1 and 47-2 should be also ruled out, and 47-0 is the only possible structure for the synthesized

p-tris(trifluoromemyl)-^j'0-te1raphenylporphyrin. In other words, the copper assisted

trifluoromethylation occurs regiospecifically at the brominated sites, and side reactions such as

rearrangement of - C F groups are unlikely.

3
 210

Fi
g ur
e 4-2. Possible isomers for P-ttis(tofluoromemyl)-wwo-tetraphenylporphyrin.
Double bonds, N , and N - H were omitted for for clarity. N and N - H are shown in
47-1' and 47-2'.
 211

Physical data of 46a, 47a, 48a, 52a, and 54a

P-
B i
s (
t
ri
fl
u or
o met
h yl
)
-5,
1 0,
1 5,
2 0-
t
e t
raphenyl
p or
p hyr
i
n (HTPP(CF)
)(46a)
: 2 32 LR-

MS (EI, 250 °C): M (m/z)

+
= 750, calcd for Q H ^ F . N , : 750.7448. UV-vis (CH.CL):

A. m a x (nm) (logs) 424 (5.49), 524 (4.19), 601 (3.62), 661 (3.86). 1 9
F N M R (CDCL): 5 (vs. CFCL)

-52.7 (s), -52.8 (s).

7,
8 47-
T r
i
s (
tr
if
l
u of
o met
h yl
)
-5,
1 0
15,
2 0-
tet
faphenyl
p or
p hyt
i
n (
H TPP(
C F
)3)(
4 7
)a)
: 2 3

L R - M S (EI, 250 °C): M (m/z) +

= 818, calcd for C H F N : 4 7 2 7 9 4 818.7418. UV-vis (CHjCL):

^max (nm) Gogs) 440 (5.29), 550 (3.94), 590sh (3.51), 735 (4.13). ' H N M R (CDC1 ): 8 -1.73 (s,lH, 3

N H ) , -1.85 (s,lH, N H ) , 7.77 (m, 12H, phenyl-;* and m-H), 8.17 (m, 8H, phenyl-o-H), 8.70 and

8.57, 8.61 and 8.31 (2 A B q, J =5.06, 5.11 Hz, 4 H , pyrr-p-H), 8.76 (s, 1H, pyrr-P-H). F N M R
AB
1 9

(CDC1 ): 8 (vs. CFC1 ) -49.1 (m, 6F), -53.1 (s, 3F). C H N anal.(%), calcdforC H F N : C , 68.95;
3 3 4 7 2 7 9 4

H , 3.32; N , 6.84, found: C, 68.71; H , 3.38; N , 6.54.

7,
8 ^748-
T et
raki
s (
t
ri
f
luor
o met
h yl
)
-5,
1 0,
1 5,
2 0-
t
e t
raphenyl
p or
p hyr
i
n (HTPP(CF
2 )
) 34

(
4 8a)
: L R - M S (EI, 250 °C): M (m/z)= 887, calcd for C H F N : 886.7388. UV-vis (CH.CL):
+
4 8 2 6 1 2 4

A. max (nm) dog s) 444(5.04), 463 (4.96), 580(3.81), 620sh (3.38), 832(4.23); (QFLJ:

^max (nm) doge) 446 (5.11), 466 (5.03), 577 (3.94), 616sh (3.48), 822 (4.32). ' H N M R ( Q D ^ : 8

-1.42(s, 2 H , N H ) , 7.45 (m, 12H, phenyl-/* and p-H), 8.00 (s, 4 H , pyrr-p-H), 8.11 (m, 4 H , phenyl-

o-H), 8.13 (m, 4 H , phenyl-o-H); ( C F C 0 D ) : 8 8.16 (m, 12H, phenyl-^ and p-H), 8.28 (s, 4 H ,
3 2

pyrr-P-H), 8.55 (s, 8H, phenyl-o-H). . F N M R (QD^),: 8 (itr. CFC1 ) -49.6 (s). C H N anal.(%),
1 9
3

calcd for C H F N : C, 65.02; H , 2.96; N , 6.32, found: C, 65.00; H , 2.86; N , 6.17.

4 8 2 6 1 2 4
 212

7,
8 ,
1 7-
T r
i
s (
t
ri
fl
u or
o met
h yl
)
-18-
^

(HTPP(CF)(CFCF)) (
2 5 2a
3)
: L R - M S (EI, 250 °C): M ( m / z ) = 936, calcd for C H F N :
3 2 3
+
4 9 2 6 1 4 4

936.7458. UV-vis (CH^l,): X m a x (nm) (log s) 444(5.03), 468(5.01), 586(3.90), 628(3.55),

844 (4.36). H N M R ( Q D ^ : 5 -1.27 (s, I H , N H ) , -1.03 (s, I H , N H ) , 7.44 (m, 12H, phenyl m and
5

p-H), 7.92 (d, I H , pyrr-P-H), 7.96 (d, I H , pyrr-P-H), 8.03 (m, 8H, phenyl o-H), 8.22 (br d (maybe

overlapped two doublets), 2H, pyrr-P-H), in addition to these porphyrin peaks there were two

sharp peaks at 1.40 (s, 2H) and 1.60 (s, 2H). These peaks diminish when D 0 is added. So 2

possibly these peaks are due to water. A residual water peak also appears at 0.4 ppm as usual case

for the ' H N M R spectrum for C D . 6 6

, 9
F N M R (QD,),: 6 (vs. CFC1 ) -47.7 (m, 3F), -49.6 (m, 6F),
3

-82.3 (m, 3F), -98.2 (m, 2F). C H N anal.(%), calcd for C H F N - 0 . 7 5 C H : C , 53.18; H , 2.43; N ,
49 26 14 4 6 6

5.64, found: C , 53.25; H , 2.54; N , 5.42.

5
4a: L R - M S (+LSIMS): M (m/z) +
= 987, calcd. for C H F N :
5 0 2 6 1 6 4 986.7528.

UV-vis (CF^CL): X miLX (nm) 444, 486, 588, 648.

Color observation (in solid): 46a; purple, 47a; brown, 48a and 52a; golden brown in solid.

48a and 52a are tangerine in color in C H C 1 containing T F A (0.5 %). 2 2

2,
3 ,
1 2,
1 3-
T et
t
a ki
s (
t
ri
fl
u of
o met
h yl
)
-5,
1 0,
1 5,
2 0-
t
e t
i
a phenyl
p or
p hyr
m at
o z
inc(
II
)

(
Z n(
T PP(
C F)
) (
4 8b)
. Z n ( O A c ) - 2 H 0 (37 mg, 0.17 mmol) in M e O H (10 mL) was added to a
3
4 2 2

brown suspension of H T P P ( C F ) (
48a
) (50 mg, 0.056 mmol) in C H C l ( 1 0 m L )
2 3 4 3 at room

temperature. The color instandy changed to a bright green and solids were completely dissolved.

The mixture was stirred for 30 min at room temperature, then CHC1 (100 mL) was added and 3

the mixture was then washed with water (2 x 100 mL). The volume of the green CHC1 solution 3

was reduced in vacuo and dried over anhydrous N a S 0 . Filtration and removal of the solvent2 4
 213

gave a green powder of 48b. The yield was 52 mg (98 %). UV-Vis (CHjCL): k mm (nm) (log e)

442 (5.37), 662 (4.31). I H N M R (CDC1 ): 8 7.70 (m, 12H, phenyl-w and p-H), 8.07 (m, 8H,
3

phenyl-o-H), 8.43 (s, 4 H , pyrr-p-H). F N M R (CDC1 ): 5 (vs. CFC1 ) -48.3. C H N anal.(%), calcd
1 9
3 3

for C ^ H ^ F ^ N . Z n : C , 60.68; H , 2.55; N , 5.90, found: C , 60.60; H , 2.56; N , 5.75.

2,3,12,13-Tettalds(trifluofomethyl)-5,10,15,20-tetraphenylpotphyfinatocobalt(II)

( C o ( T P P ( C F ) ) (48e).
3 4 H T P P ( C F ) (48a) (50 mg, 0.056 mmol)
2 3 4 and C H C l ( 1 0 m L )
3 were

placed in a 50 mL-round-bottomed flask. C o C l (22 mg, 0.17 mmol) in M e O H ( l O m L )

2 was

added to the brown suspension in the flask and the mixture was refluxed for 30 min. The color

of the solution changed from brown to bright green. The green solution was diluted with

CHC1 (100 mL) and washed with water (2 x 100 mL). The amount of the green CHC1 solution
3 3

was reduced in vacuo and dried over anhydrous N a S 0 . Filtration and removal of the solvent 2 4

gave a green powder of 48e. The yield was 51 mg (96 %). H R - M S (EI, 220 °C): M (m/z) = +

943.11455 (100%), calcd for C H F N C o : 943.11413. UV-Vis

4 8 2 4 1 2 4 (CPLjjL): X max (nm) (log s)

440(5.06), 636 (4.32). ' H N M R (CDC1 ): 8 9.55 (m, 12H, phenyl-/*? and p-H), 13.57 (bs, 8H,
3

phenyl-o-H), 15.41 (bs, 4H, pyrr-p-H). 1 9

F N M R (CDC1 ): 8 (vs. CFCL) -54.3. C H N anal.(%),
3

calcd for C H F N C o : C , 61.09; H , 2.56; N , 5.94, found: C , 61.41; H , 2.62; N , 5.78.

4 8 2 4 1 2 4

Chloro(2,3,12,13-tetiakis(trifluoromethyl)-5,10,15,20-

tettaphenylporphyrinato)iton(III) ( F e ( T P P ( C F ) ) C l ) (48f).
3 4 H T P P ( C F ) (48a) (45.3 mg,
2 3 4

0.0511 mmol) and lithum bis(trimethylsilyl)amide (122.2 mg, 0.730 mmol) were dissolved in dry

T H F (4.5 mL) at room temperature under N . The color of the solution became dark orange.
2

The solution was stirred for 5 min in a septum-sealed flask. Under an N atmosphere anhydrous 2

FeCl (87.2 mg, 0.692 mmol) was added to the solution. The mixture was then warmed at 50°C.
2
 214

The color of the solution gradually changed to dark green in 3 min. The solution was stirred

under N 2 at room temperature for 2 h. The color further changed to brighter green. T L C using

an alumina plate (CH Cl /petroleum ether = 50/50(v/v)) showed a weak brown spot moving
2 2

fastest and a major green band smearing from the origin. After the solvent was removed from

the reaction mixture, the product was dissolved in CH Cl /petroleum ether (50/50 (v/v)(10 mL) 2 2

and was chromatographed on an acidic alumina column. The green color of the compound

turned brown on the column. The first fraction was identified as the u—oxodimer

(Fe(TPP(CF ) ] 0 (61) from mass spectrometry. The slow moving green fraction was washed
3 4 2

with acetone and combined with the Li-oxodimer (61). The solvent was removed, the product

was dissolved in C H C 1 (50 mL) and washed with cold 6 M HC1 (50 mL) until the organic phase
2 2

turned bright green. The C H C 1 2 2 phase was collected and dried over anhydrous N a S 0 . 2 4

Filtration and removal of the solvent gave a dark blue powder of 48f (31.0mg, 62.3%).

Fe((TPP(CF ) )Cl (48f): L R - M S (+LSIMS): M ( m / z ) = 940, calcd. for C H F N F e : 940.5728.

3 4
+
4 8 2 4 1 2 4

UV-Vis (CH CL): 2 A. m a x (nm) (log 8) 452(4.76), 618(4.12). ' H N M R (CDCL): 5 4.04 (s, 4 H ,

phenyl-^-H), 6.5 - 3.5 (bs, 8H, phenyl-o-H), 14.52 (s, 8H, phenyl-w-H), 77.15 (bs, pyrr-p-H, 4H).

1 9
F N M R (CDC1 ): 8 (vs. CFCL) 0.05 (s).
3 [Fe(TPP(CF ) ] 0 (61): L R - M S (+LSIMS): M ( m / z ) =
3 4 2
+

1897 (93 %), 940 (100%), calcd. for C H F N OFe :

% 4 8 2 4 8 2 1897.145. UV-Vis (CH.CL):

?Vax (nm) (relative intensity) 435 (1.0), 700 (0.3). ' H N M R (CDC1 ): 8 6.55 (bs, 8H, phenyl-H), 3

7.36 (bs, 8H, phenyl-H), 7.72 - 8.12 (m, 24H, phenyl-H), 11.52 (bs, 4 H , pyrr-p-H), 12.19 (bs, 4 H ,

pyrr-p-H). , 9
F N M R (CDCL): 8 (vs. CFC1 ) -46.8 (s. 12F),-45.2 (s, 12F). 3

Chloro(23,12-tris(trifluoromethyl)-13-pentafluoroethyl-5,10,15,20-

tetraphenylporphyrinato)iron(III) ( F e ( T P P ( C F ) ( C F C F ) ) C l ) (52c). This porphyrin was 3 3 2 3

synthesized in a similar method as for the synthesis of Fe((TPP(CF ) )Cl (48f). The yield was 3 4
 215

42mg(76% based on 50 mg of 52a)

. L R - M S (+LSIMS): M ( m / z ) +
= 940, calcd. for

C^H^N.Fe: 940.5728. UV-Vis (CH.CL): A. MAX (nm) (log e) 452(4.76), 618(4.12). ' H N M R

(CDCL): 5 3.10 (m, 4 H , phenyl-^-H), 4.80 (bs, 8 H , phenyl-o-H), 14.75 (s, 2 H , phenyl-w-H),

15.22 (s, 6 H , phenyl-^-H), 73.52 (bs, 1H, pyrr-p-H), 74.65 (bs, 3 H , pyrr-p-H). 1 9
F N M R (CDC1 ): 3

5 (vs. CFC1 ) -66.3 (s, 3F), -13.8 (b, 2F), -6.2 (s, 3F), 1.1 (s, 3F), 14.5 (s, 3F).
3

P-
M et
h yl
-
m eso-
t
e t
raphenyl
p or
p hyr
i
n s. CuBr (l.OOg ,7 mmol) and C H L i ( 1 0 m L 3 of

1.4 M solution in Et 0,14 mmol) were mixed at -80 °C under N in a flame-dried 50-mL one-
2 2

neck round-bottomed flask with a stopcock side arm that was sealed with a rubber septum. The

mixture was stirred at - 8 0 ° C under N 2 until the CuBr was dissolved completely.

Zn(TPPBr ) (
4
45b) (233 mg , 0.235 mmol) was added under a N 2 stream to the solution. The

color of the mixture became green instandy. The solution was kept in an oil bath at 3 2 ° C . A

small amount of mixture was withdrawn with a syringe to monitor the U V - V i s spectrum of the

mixture during the reaction. The solids that built up at the edge of the solution were dissolved

using a sonicator. The reaction was run for 24 h. There was no difference in UV-Vis spectra

between 6 and 24 h. After the reaction was complete, dilute HC1 (5 mL) was carefully added.

100 m L of C H C 1 was added and the solution was washed with H 0 (100 mL). A red powder of
2 2 2

the mixture of Zn(II) porphyrins was obtained by removing CH C1 . In order to remove the —Br
2 2

groups remaining on the pyrolic P-positions, the Zn(II) porphyrins were refluxed in D M F (not

dried) in the presence of CuBr for 2 h. After this reaction was complete, D M F was evaporated.

Zn(II) porphyrins were dissolved in C H C 1 and CuBr was removed by filtration. A red powder
2 2

was obtained by removing CH C1 . Since the product was poorly soluble in common organic
2 2

solvents and a T L C investigation did not give a satisfactory result, the Zn(II) porphyrins were

then demetallated. The red powder (140 mg) was then dissolved in T F A (3 mL) and refluxed for
 216

1.5 h. Demetallation was complete as confirmed by disappearance of the Soret peak at 416 nm.

The resultant green mixture gave a broad Soret band at 446 nm and a Q band at 656 nm in

C H C 1 The mixture was cooled down to room temperature and diluted with CHC1 (100 mL).
2 2 3

The green solution was washed with H O (2 x 100 mL), with 7.5 % aq. N a H C 0z 3 (1 x 100 mL),

and with H 0 (1 x 100 mL). The amount of the CHC1 solution was reduced to ca.5 mL. Free-
2 3

base porphyrins were mixed with approximately the same amount of silica gel (70 - 230 mesh).

The silica gel was dried in air at room temperature in the fume hood. The porphyrin-preadsorbed

silica gel was placed on the top of the silica gel column prepared in CHC1 . Two fractions were 3

obtained from the column chromatography with CHC1 . 3 Each fraction contained two

compounds. The compounds in the first fraction were chromatographed on a silica gel column

with CH C1 /petroleum ether and the separation yielded H T P P ( C H ) (56a) (less than 0.5 mg)
2 2 2 3

and H T P P ( C H )
2 3 2 (57 a) (29 mg, 19 %). The remaining mixture was chromatographed on a silica

gel column with CH C1

2 2 containing 2 vol% of acetone and the separation yielded

H TPP(CH )
2 3 3 (58a) (26 mg, 17 %) and H T P P ( C H ) 2 3 4 (59a) (24 mg, 15 %).

Physical data of 56a, 57a, 58a, and 59a

p-Methyl-5,10,15,20-tettaphenylporphyrin (H TPP(CH )) (56a): L R - M S

2 3 (EI, 250 °C):

M ( m / z ) = 628, calcd. for C H N : 628.7778. UV-vis (CH^CL):

+
4 5 3 2 4 (nm) 417 (Soret), 514, 548,

588, 644.

p-Dimethyl-5,10,15,20-tettaphenylporphyrin (H TPP(CH ) ) (57a):

2 3 2 L R - M S (EI,

250 °C): M ( m / z ) = 642, calcd. for C H N : 642.8048. UV-vis (CH.Ch): X

+
4 6 3 4 4 m a x (nm) (log e)

418 (5.69), 514 (4.35), 546 (3.76), 587 (3.87), 640 (3.75).
 217

2,
3 ,
1 2-
T r
i
m et
h yl
-
5 ,
1 0,
1 5,
2 0-
t
e t
f
a phenyl
p or
p hyr
i
n (HTPP(CH)
)(58a)
: L R - M S (EI, 2 33

250 °C): M ( m / z ) = 656, calcd. for C H N : 656.8318. UV-vis (CH CL): X

+
4 7 3 4 4 2 m a x (nm) (log e)

419 (5.60), 516 (4.29), 584 (3.66), 644 (3.24). ' H N M R (CDCL): 5 -2.67 (s, 1H, N H ) , -2.94 (s, 1H,

N H ) , 2.42 (s, 3 H , - C H ) , 2.44 (s, 3H, - C H ) , 2.59 (s, 3H, - C H ) , 7.70 (m, 12H, phenyl-/* and p-H),
3 3 3

8.06 (m, 6H, phenyl-o-H), 8.17 (m, 2 H , phenyl-o-H), 8.63, 8.56 (ABq, 2 H , pyrr-p-H), 8.54 (m, 2 H ,

pyrr-P-H), 8.59 (s, 1H, pyrr-p-H). C H N anal.(%), calcd for C H N - 0 . 5 H O : C, 84.78; H , 5.68;
47 36 4 2

N , 8.41, found: C , 84.79; H , 5.43; N , 8.48.

2,
3 ,
1 2,
1 3-
T et
ramet
h yl
-
5 ,
1 0,
1 5,
2 0-
t
e t
raphenyl
p or
p hyr
i
n (HTPP(CH)
)(59a)
: LR- 2 3
4

MS (EI, 250 °C): M ( m / z ) = 670, calcd. for C H N : 670.8588. UV-vis (CH CL): X
+
4 8 3 8 4 2 m3X (nm)

420 (Soret), 520, 588, 640. H N M R (CDCL): 5 -2.77 (s, 2 H , N H ) , 2.39 (s, 12H, - C H ) , 7.71 (m,
]
3

12H, phenyl-/* and p-H), 8.07 (m, 8H, phenyl-o-H), 8.44 (s, 4 H , pyrr-P-H); ( Q D ) : 5 2.38 (s, 12H, 6

- C H ) , 7.40 (m, 12H, phenyl-/* and p-H), 7.97 (m, 8H, phenyl-o-H), 8.75 (s, 4 H , pyrr-P-H);
3

( C F C O D ) : 8 2.57 (s, 12H, - C H ) , 8.40 (m, 12H, phenyl-/* and p-H), 8.66 (s, 4 H , phenyl-o-H),
3 z 3

9.01 (s, 4 H , phenyl-o-H), 8.80 (s, 4H, pyrr-p-H). C H N anal.(%), calcd for C^H^N.-O.SCHCL,: C,

79.73; H , 5.31; N , 7.67, found: C, 79.35; H , 5.31; N , 7.41.

Color obsevations: 57a, 58a, and 59a were purple in the solid phase and green in C H C 1 2 2

containing 0.5 % T F A .

2,
3 ,
1 2,
1 3-
T et
ramet
h yl
-
5 ,
1 0,
1 5,
2 0-
t
e t
raphenyl
p or
p hyr
i
n at
o z
i
n c(
I
)(Zn(
T PP(
C H)
)) 3
4

(
5 9b)
. Zn(TPP(CH ) ) (59a) 3 4 (20 mg, 0.030 mmol) was dissolved in CHCl (20mL). 3

Z n ( O A c ) - 2 H 0 (20 mg, 0.091 mmol) was dissolved in M e O H (10 mL) and added to the CHC1
2 2 3

solution of porphyrin. The mixture was refluxed for 1 h. The color of the solution changed from
 218

purple to red. After the solvents were removed by a rotary evaporator, the product was dissolved

in CHCI3 (60 mL) and washed with water (3 x 60 mL). The solution was dried using anhydrous

N a S 0 . Filtration and evaporation of the CHC1 solution yielded a red powder of 59b (18 mg,
3 4 3

80%). L R - M S (EI): M ( m / z ) = 732, calcd. for C H , N Z n : 732.7718 (63.929 (

+
"Zn) for Zn).
4 8 3 4

UV-vis (CHjCh): X max (nm) 420 (5.63), 534sh (3.99), 551 (4.26), 587sh (3.64). ' H N M R (CDC1 ): 3

8 2.34 (s, 12H, - C H ) , 7.75 (m, 12H, phenyl-**?

3 and.p-H), 8.06 (m, 8H, phenyl-o-H), 8.65 (s, 4 H ,

pyrr-P-H).

Cr
y st
a l
s for X-
ray cr
y st
a l
o gr
a phy. Zn(
T PPBr
)•(
M e
O H)•(
D MF)
. Zn(TPPBr ) (45b) 4 4

was completely dissolved in hot D M F and the solution was cooled to room temperature. The

same volume of M e O H was layered on top of the porphyrin solution. After a period of 1 — 2

days shiny chip crystals were obtained. ' H N M R could not be measured in CDC1 because of the 3

low solubility of the crystals. ' H N M R (DMSO-d^: 8 2.75 (s, 3H, D M F (-CH,)), 2.89 (s, 3 H ,

D M F (-CHj)), 3.22 (d, 3H, M e O H (-CH )), 4.08 (q, I H , M e O H (-OH)), 7.78 (m, 12H, phenyl-^
3

and p-H), 7.99 (s, I H , D M F (-CHO)), 8.02 (m, 8H, phenyl-o-H), 8.60 (s, 4 H , pyrr-P-H). C H N

anal.(%), calcd for C H B r N 0 Z n (45b-(MeOH)-(DMF)): C , 52.47; H , 3.21; N , 6.37, found:

4 8 3 5 4 5 2

52.32; H , 3.17; N , 6.02.

Zn(TPP(CF)
)(EtOH)
. Zn(TPP(CF ) ) (48b)
3
4 3 3 4 was dissolved in C H C l / E t O H
3

(50/50 (v/v)) at room temperature. After period of two weeks, purple prism crystals were

obtained by slow evaporation of the solvents at room temperature. H N M R ( C D C y : 8 0:34 (t,

3H, E t O H (-OH)), 0.73 (t, 9 H , E t O H (-CH,)), 2.94 (m, 6H, E t O H (-CH -)), 7.70 (m, 12H, 2

19

phenyl-*? and p-H), 8.08 (m, 8H, phenyl-o-H), 8.37 (s, 4H, pyrr-p-H). F N M R (CDC1 ): 8 (vs.
3

CFC1 ) -48.36. UV-vis ( C H C y X

3 2 max (nm) (log e): 444(5.42), 598sh (3.82), 664(4.34). C H N
 219

anal.(%), calcd for C H F N Z n 0 (48b-(EtOH)), C , 59.60; H , 3.89; N , 5.15, found: C , 60.00;

5 4 4 2 1 2 4 3 3

H , 3.64; N , 5.02.

Zn(
T PP(
C H)
)(THF)
-(CHCl
). 34 6
1 34
0 ZnCTPP(CH ) ) (59b)
3 4 was dissolved i n

C H C 1 / T H F (50/50 (v/v)) at room temperature. After a period of a week, red needle crystals
3

were obtained by slow evaporation of the solvents at room temperature. *H N M R (CDjCL): 5

I. 76 (m, T H F ) , 2,37 (s, H 0 ) , 3.56 (m, T H F ) , 7.32 (s, CHC1 ), 7.75 (m, 12H, phenyl-/* and p-H),
2 3

8.06 (m, 8H, phenyl-o-H), 8.65 (s, 4 H , pyrr-p-H). C H N anal.(%), calcd for C 5 4 8 H 4 9 2 C1 N 0, Zn
1 2 4 6

(59b-(THF) -(CHCl ) ), C , 73.35; H , 5.53; N , 6.24, found: C , 73.15; H , 5.60; N , 6.06.

16 3 04
 220

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 APPENDC
IES

A. UV-
v i
s i
b l
espe
ctr
a of di
a ci
d s of 48a and 59a

<

0
300 4
00 5
00 6
00 7
00 8
00 9
00 1
000
2
5
.E+
05

2
0
.E+
05

1
5
.E+
05
a

CO
1
0
.E+
05

5
0
.E+
04 4

0
0
.E+
00 -I 1 1 1 1 1 1
— ^— H
3
00 4
00 50
0 60
0 70
0 80
0 9 00 1
000

Wavelength (nm)

Fi
g ur
e A-l. UV-visible spectra of freebase porphyrins, H T P P ( C F )
2 3 4 (48a)
and H T P P ( C H ) (
2 3 459a
) in C H C 1 and their diacids in C H C 1 containing
2 2 2 2

0.5 %(v) T F A . The Q bands are shown in five times magnification.

 234

B. Crystallographic Data

Table B-l-a. Atomic coordinates and B„forZn(TPP(CF ) )-(EtOH)

3 4 3

atom X y z K
Zn© 0.40652(4) 0.45182(3) 0.27515(2) 2.105(9)
F(l) -0.0024(2) 0.6348(2) 0.17616(14) 5.05(7)
F(2) 0.1343(2) 0.7873(2) 0.25687(13) 4.76(7)
F(3) 0.0886(2) 0.7600(2) 0.12336(12) 4.59(7)
F(4) 0.0857(2) 0.6128(2) 0.01207(12) 4.21(6)
F(5) 0.2337(2) 0.7615(2) 0.02916(12) 4.45(6)
F(6) 0.2514(2) 0.6072(2) -0.00580(1) 3.80(6)
F(7) 0.5928(2) 0.1348(2) 0.19573(11) 4.27(6)
F(8) 0.6770(2) 0.0913(2) 0.31178(13) 4.28(6)
F(9) 0.4803(2) 0.0155(2) 0.23892(13) 4.55(6)
F(10) 0.3258(3) 0.0129(2) 0.35462(14) 5.28(7)
F(ll) 0.4561(2) 0.1002(2) 0.48003(12) 4.25(6)
F(12) 0.5179(2) 0.0247(2) 0.39364(15) 5.72(8)
0(1) 0.2500(3) 0.3304(2) 0.17867(15) 3.47(7)
0(2) 0.1471(4) 0.1289(3) . 0.1850(2) 8.52(12)
0(3) -0.0946(6) 0.0432(6) 0.1786(5) 17.6(3)
N© 0.3575(3) 0.5874(2) 0.24406(15) 2.20(7)
N(2) 0.5318(3) 0.4892(2) 0.21806(15) 2.16(7)
N(3) 0.4884(2) 0.3448(2) 0.33033(15) 1.86(6)
N(4) 0.3399(2) 0.4618(2) 0.36900(14) 2.04(6)
C© 0.2669(3) 0.6174(3) 0.2632(2) 2.13(8)
C(2) 0.2081(3) 0.6642(3) 0.1953(2) 2.40(8)
C(3) 0.2633(3) 0.6573(3) 0.1361(2) 2.47(8)
C(4) 0.3642(3) 0.6183(3) 0.1702(2) 2.11(8)
C(5) 0.4671(3) 0.6248(3) 0.1460(2) 2.15(8)
C(6) 0.5511(3) 0.5719(3) 0.1758(2) 2.13(8)
C(7) 0.6700(3) 0.5931(3) 0.1655(2) 2.78(9)
C(8) 0.7205(3) 0.5242(3) 0.1999(2) 2.88(9)
C(9) 0.6330(3) 0.4561(3) 0.2308(2) 2.20(8)
C(10) 0.6454(3) 0.3656(3) 0.2631(2) 2.25(8)
C(ll) 0.5600(3) 0.3027(3) 0.2980(2) 2.04(8)
C(12) 0.5460(3) 0.1964(3) 0.3140(2) 2.22(8)
C(13) 0.4765(3) 0.1810(3) 0.3648(2) 2.18(8)
C(14) 0.4393(3) 0.2754(3) 0.3749(2) 1.96(8)
C(15) 0.3732(3) 0.3039(3) 0.4245(2) 1.78(7)
C(16) 0.3394(3) 0.3954(3) 0.4261(2) 2.01(8)
C(17) 0.2878(3) 0.4319(3) 0.4858(2) 2.49(8)
C(18) 0.2550(3) 0.5155(3) 0.4642(2) 2.77(9)
(continued)
 235

Table B-l-a (continued)

atom X y z
C(19) 0.2818(3) 0.5319(3) 0.3870(2) 2.06(8)
C(20) 0.2427(3) 0.6006(3) 0.3387(2) 2.18(8)
C(21) 0.1079(4) 0.7096(3) 0.1883(2) 3.27(10)
C(22) 0.2101(4) 0.6614(3) 0.0437(2) 3.26(10)
C(23) 0.5764(4) 0.1102(3) 0.2673(2) 3.07(10)
C(24) 0.4430(4) 0.0796(3) 0.3977(2) 3.16(10)
C(25) 0.4989(3) 0.7049(3) 0.0941(2) 2.24(8)
C(26) 0.5115(3) 0.8111(3) 0.1200(2) 2.75(9)
C(27) 0.5424(4) 0.8870(3) 0.0731(2) 3.45(10)
C(28) 0.5577(4) 0.8543(3) -0.0023(2) 3.35(10)
C(29) 0.5462(4) 0.7497(3) -0.0297(2) 3.12(10)
C(30) 0.5171(3) 0.6737(3) 0.0178(2) 2.69(9)
C(31) 0.7586(3) 0.3389(3) 0.2678(2) 2.41(8)
C(32) 0.7922(4) 0.3252(3) 0.1960(2) 3.37(10)
C(33) 0.9020(4) 0.3082(4) 0.2033(2) 4.34(12)
C(34) 0.9799(4) 0.3025(4) 0.2804(3) 4.26(12)
C(35) 0.9455(4) 0.3125(3) 0.3518(2) 3.42(10)
C(36) 0.8361(3) 0.3308(3) 0.3448(2) 2.64(9)
C(37) 0.3268(3) 0.2326(3) 0.4786(2) 2.22(8)
C(38) 0.2116(3) 0.1517(3) 0.4429(2) 2.85(9)
C(39) 0.1627(4) 0.0876(3) 0.4918(3) 4.26(12)
C(40) 0.2295(5) 0.1089(4) 0.5784(3) 4.91(14)
C(41) 0.3432(5) 0.1917(4) 0.6161(2) 4.70(13)
C(42) 0.3923(4) 0.2548(3) 0.5662(2) 3.48(10)
C(43) 0.1717(3) 0.6601(3) 0.3729(2) 2.49(9)
C(44) 0.0479(4) 0.6083(3) 0.3607(2) 3.37(10)
C(45) -0.0117(4) 0.6642(4) 0.3981(3) 4.57(13)
C(46) 0.0512(5) 0.7673(5) 0.4467(3) 5.19(15)
C(47) 0.1739(5) 0.8170(4) 0.4596(2) 5.00(13)
C(48) 0.2353(4) 0.7654(3) 0.4231(2) 3.76(10)
C(49) 0.1611(3) 0.3458(3) 0.1053(2) 317(9)
C(50) 0.2063(4) 0.3502(4) 0.0323(2) 4.58(12)
C(51) 0.1920(10) 0.0529(7) 0.1521(5) 13.4(3)
C(52) 0.1820(14) 0.0259(12) 0.0790(8) 21.2(7)
C(53) -0.1280(8) -0.0194(10) 0.2344(6) 14.0(4)
C(54) -0.0855(10) .-0.1019(7) 0.2312(7) 16.8(4)

Equivalent temperature factor:

Btq = 3 7t (U„(aa*) +
2 2
U (bb*) + U (cc*) +
22
2
33
z
2(7 aa*bb*cosY + 2L/ aa*cc*cos|3 +
12 13

2L/ bb*cc*cosa) [Refer to the end of Table B-3-b for the parameters.]
23
 236

Table B-l-b. A n i s o t r o p i c displacement parameters for Z n ( T P P ( C F ) ) ' ( E t O H ) .

3 4 3

atom U n
rj 3
3 u„ U i3
ua

Zn© 0.0361(3) 0.0268(2) 0.0254(2) 0.0155(2) 0.0156(2) 0.0129(2)

F© 0.0400(15) 0.088(2) 0.078(2) 0.0266(15) 0.0281(13) 0.0414(15)
F(2) 0.090(2) 0.070(2) 0.0491(13) 0.062(2) 0.0283(14) 0.0210(12)
F(3) 0.076(2) 0.087(2) 0.0524(13) 0.062(2) 0.0358(13) 0.0464(13)
F(4) 0.0395(15) 0.080(2) 0.0386(12) 0.0219(14) 0.0074(11) 0.0246(12)
F(5) 0.073(2) 0.067(2) 0.0491(13) 0.0390(14) 0.0249(13) 0.0416(12)
F(6) 0.0579(15) 0.067(2) 0.0270(10) 0.0314(13) 0.0150(11) 0.0170(10)
F(7) 0.105(2) 0.0460(15) 0.0390(11) 0.0425(14) 0.0449(13) 0.0198(10)
F(8) 0.077(2) 0.057(2) 0.0610(14) 0.0496(14) 0.0385(14) 0.0281(12)
F(9) 0.077(2) 0.0292(14) 0.0729(15) 0.0187(14) 0.0379(15) 0.0077(12)
F(10) 0.079(2) 0.0362(15) 0.074(2) 0.0003(15) 0.031(2) 0.0186(13)
F(ll) 0.083(2) 0.065(2) 0.0502(13) 0.0473(15) 0.0420(13) 0.0448(12)
F(12) 0.127(2) 0.066(2) 0.099(2) 0.075(2) 0.084(2) 0.064(2)
O(l) 0.045(2) 0.039(2) 0.0336(14) 0.0048(15) 0.0036(13) 0.0121(12)
0(2) 0.113(3) 0.045(3) 0.129(3) 0.002(2) 0.018(3) 0.028(2)
0(3) 0.203(7) 0.207(7) 0.317(8) 0.089(6) 0.121(6) 0.160(7)
N(l) 0.042(2) 0.028(2) 0.0274(14) 0.0200(15) 0.0206(14) 0.0155(12)
N(2) 0.040(2) 0.026(2) 0.0287(14) 0.0202(15) 0.0176(14) 0.0162(13)
N(3) 0.029(2) 0.024(2) 0.0267(14) 0.0136(14) 0.0154(13) 0.0159(12)
N(4) 0.036(2) 0.027(2) 0.0245(14) 0.0192(15) 0.0143(14) 0.0152(12)
C© 0.031(2) 0.027(2) 0.029(2) 0.015(2) 0.012(2) 0.0121(15)
C(2) 0.038(2) 0.036(2) 0.032(2) 0.023(2) 0.018(2) 0.021(2)
C(3) 0.041(2) 0.036(2) 0.026(2) 0.020(2) 0.015(2) 0.018(2)
C(4) 0.042(2) 0.021(2) 0.025(2) 0.015(2) 0.015(2) 0.0133(15)
C(5) 0.034(2) 0.024(2) 0.027(2) 0.012(2) 0.012(2) 0.0134(15)
C(6) 0.036(2) 0.028(2) 0.027(2) 0.015(2) 0.017(2) 0.0148(15)
C(7) 0.037(2) 0.038(2) 0.043(2) 0.015(2) 0.025(2) 0.024(2)
C(8) 0.031(2) 0.050(3) 0.046(2) 0.023(2) 0.023(2) 0.030(2)
C(9) 0.035(2) 0.030(2) 0.024(2) 0.014(2) 0.013(2) 0.0135(15)
C(10) 0.036(2) 0.030(2) 0.028(2) 0.017(2) 0.016(2) 0.0138(15)
C(ll) 0.031(2) 0.031(2) 0.023(2) 0.017(2) 0.012(2) 0.0133(15)
C(12) 0.040(2) 0.023(2) 0.032(2) 0.019(2) 0.018(2) 0.0129(15)
C(13) 0.036(2) 0.027(2) 0.027(2) 0.016(2) 0.012(2) 0.0174(15)
C(14) 0.035(2) 0.022(2) 0.021(2) 0.011(2) 0.012(2) 0.0137(14)
C(15) 0.027(2) 0.023(2) 0.022(2) 0.011(2) 0.0096(15) 0.0124(14)
C(16) 0.028(2) 0.027(2) 0.022(2) 0.009(2) 0.011(2) 0.0098(15)
C(17) 0.038(2) 0.038(2) 0.028(2) 0.019(2) 0.016(2) 0.013(2)
C(18) 0.053(3) 0.036(2) 0.028(2) 0.023(2) 0.022(2) 0.011(2)
C(19) 0.031(2) 0.023(2) 0.023(2) 0.009(2) 0.011(2) 0.0040(14)
C(20) 0.035(2) 0.025(2) 0.029(2) 0.015(2) 0.016(2) 0.0108(15)
C(21) 0.055(3) 0.052(3) 0.034(2) 0.033(2) 0.020(2) 0.022(2)
C(22) 0.039(3) 0.051(3) 0.039(2) 0.021(2) 0.013(2) 0.022(2)
C(23) 0.056(3) 0.033(3) 0.039(2) 0.022(2) 0.023(2) 0.016(2)
C(24) 0.057(3) 0.033(3) 0.051(2) 0.027(2) 0.033(2) 0.021(2)
(continued)
 237

Table B-l-b. (continued)

atom
C(25) 0.034(2)
ua

0.031(2)
rj33
0.025(2)
L712

0.016(2)
u„
0.010(2)
ua

0.0150(15)
C(26) 0.055(3) 0.028(2) 0.034(2) 0.024(2) 0.020(2) 0.015(2)
C(27) 0.070(3) 0.030(2) 0.044(2) 0.027(2) 0.025(2) 0.020(2)
C(28) 0.064(3) 0.038(3) 0.039(2) 0.024(2) 0.024(2) 0.028(2)
C(29) 0.055(3) 0.043(3) 0.035(2) 0.025(2) 0.025(2) 0.021(2)
C(30) 0.054(3) 0.030(2) 0.031(2) 0.024(2) 0.023(2) 0.015(2)
C(31) 0.038(2) 0.034(2) 0.031(2) 0.019(2) 0.019(2) 0.018(2)
C(32) 0.055(3) 0.069(3) 0.030(2) 0.042(2) 0.025(2) 0.029(2)
C(33) 0.067(3) 0.089(4) 0.052(3) 0.054(3) 0.044(3) 0.041(2)
C(34) 0.056(3) 0.076(3) 0.068(3) 0.049(3) 0.041(3) 0.040(3)
C(35) 0.049(3) 0.047(3) 0.046(2) 0.028(2) 0.017(2) 0.027(2)
C(36) 0.036(2) 0.037(2) 0.035(2) 0.017(2) 0.017(2) 0.018(2)
C(37) 0.035(2) 0.030(2) 0.032(2) 0.017(2) 0.019(2) 0.018(2)
C(38) 0.038(2) 0.033(2) 0.043(2) 0.014(2) 0.018(2) 0.017(2)
C(39) 0.056(3) 0.040(3) 0.090(3) 0.020(2) 0.050(3) 0.033(2)
C(40) 0.102(4) 0.055(3) 0.076(3) 0.041(3) 0.072(3) 0.045(3)
C(41) 0.101(4) 0.058(3) 0.038(2) 0.034(3) 0.038(3) 0.028(2)
C(42) 0.064(3) 0.035(2) 0.031(2) 0.013(2) 0.015(2) 0.016(2)
C(43) 0.047(3) 0.033(2) 0.027(2) 0.024(2) 0.018(2) 0.016(2)
C(44) 0.048(3) 0.051(3) 0.050(2) 0.029(2) 0.029(2) 0.024(2)
C(45) 0.074(3) 0.071(4) 0.064(3) 0.047(3) 0.043(3) 0.038(3)
C(46) 0.114(5) 0.093(4) 0.048(3) 0.087(4) 0.050(3) 0.038(3)
C(47) 0.099(4) 0.056(3) 0.045(3) 0.051(3) 0.019(3) 0.003(2)
C(48) 0.064(3) 0.041(3) 0.042(2) 0.028(2) 0.015(2) 0.007(2)
C(49) 0.034(2) 0.043(3) 0.039(2) 0.015(2) 0.007(2) 0.008(2)
C(50) 0.072(3) 0.076(4) 0.037(2) 0.036(3) 0.022(2) 0.021(2)
C(51) 0.243(11) 0.110(7) 0.119(6) 0.109(8) -0.021(6) 0.017(6)
C(52) 0.46(2) 0.32(2) 0.280(12) 0.28(2) 0.29(2) 0.229(14)
C(53) 0.166(9) 0.228(12) 0.193(8) 0.070(8) 0.115(7) 0.114(8)
C(54) 0.287(13) 0.110(7) 0.363(13) 0.146(9) 0.199(11) 0.074(8)

The general temperature factor expression:

exp(-27l (a* £V + b* U k + c* Uj
2 2 2 2
22
2 2
+ 2a*b*[/ M + 2a*c*[/ />/ + 2b*c*U >fe/
12 13 23

[Refer to the end of Table B-3-b for parameters.]

 238

T a b l e B-2-a. Atomic coordinates and B„ for Zn(TPPBr )-(MeOH>pMF)

4

atom x y_ z ffeq

Br© 0.58180(4) -0.04914(3) 0.69092(3) 1.875(8)

Br(2) 0.53182(4) -0.28795(3) 0.74241(3) 2.238(8)
Br(3) 0.72294(5) -0.43406(3) -0.07081(3) 3.16(1)
Br(4) 0.68507(4) -0.17764(3) -0.11018(3) 2.351(9)
Zn® 0.74243(3) -0.26443(3) 0.29861(3) 0.925(7)
O(l) 0.9292(2) -0.3092(2) 0.2706(2) 1.84(5)
0(2) 0.9950(3) -0.4945(3) 0.3487(3) 4.26(9)
N© 0.6918(2) -0.2356(2) 0.4507(2) 0.97(5)
N(2) 0.7148(2) -0.4077(2) 0.3328(2) 0.99(5)
N(3) 0.7404(3) -0.2803(2) 0.1550(2) 1.13(6)
N(4) 0.7244(3) -0.1109(2) 0.2710(2) 1.05(5)
N(5) 1.0279(3) -0.6695(3) 0.3602(3) 3.14(9)
C© 0.6800(3) -0.1434(2) 0.4904(2) 0.98(6)
C(2) 0.6312(3) -0.1512(2) 0.5963(2) 1.11(6)
C(3) 0.6151(3) -0.2480(3) 0.6173(2) 1.15(6)
C(4) 0.6568(3) -0.3030(2) 0.5260(2) 0.84(6)
C(5) 0.6689(3) -0.4089(2) 0.5139(2) 0.99(6)
C(6) 0.6999(3) -0.4559(2) 0.4234(2) 0.95(6)
C(7) 0.7228(3) -0.5660(2) 0.4117(3) 1.25(7)
C(8) 0.7493(3) -0.5831(2) 0.3158(3) 1.35(7)
C(9) 0.7437(3) -0.4831(2) 0.2656(2) 0.97(6)
C(10) 0.7598(3) -0.4684(2) 0.1650(3) 1.28(7)
C(ll) 0.7470(3) -0.3717(3) 0.1150(2) 1.21(7)
C(12) 0.7347(3) -0.3479(3) 0.0177(3) 1.61(7)
C(13) 0.7220(3) -0.2456(3) 0.0008(3) 1.52(7)
C(14) 0.7313(3) -0.2030(3) 0.0852(2) 1.12(6)
C(15) 0.7386(3) -0.1024(2) 0.0951(3) 1.28(7)
C(16) 0.7412(3) -0.0631(2) 0.1808(3) 1.25(7)
C(17) 0.7598(4) 0.0378(3) 0.1855(3) 1.78(8)
C(18) 0.7536(3) 0.0495(3) 0.2790(3) 1.52(7)
C(19) 0.7291(3) -0.0423(2) 0.3331(3) 1.19(7)
C(20) 0.7082(3) -0.0561(2) 0.4349(2) 1.05(6)
C(21) 0.6585(3) -0.4795(2) 0.6026(2) 0.94(6)
C(22) 0.7444(3) -0.4985(3) 0.6507(3) 1.35(7)
C(23) 0.7353(4) -0.5599(3) 0.7349(3) 1.81(8)
C(24) 0.6404(4) -0.6046(3) 0.7719(3) 1.75(7)
C(25) 0.5561(3) -0.5885(3) 0.7234(3) 1.67(7)
C(26) 0.5650(3) -0.5263(3) 0.6385(3) 1.25(7)
C(27) 0.7910(3) -0.5649(3) 0.1069(3) 1.40(7)
C(28) 0.7039(4) -0.6128(3) 0.1091(3) 2.23(8) •
C(29) 0.7328(4) -0.7001(3) 0.0536(3) 2.81(9)
C(30) 0.8487(5) -0.7402(3) -0.0030(3) 3.1(1)
C(31) 0.9364(4) -0.6944(3) -0.0061(3) 2.92(9)
C(32) 0.9075(4) -0.6062(3) 0.0505(3) 2.10(8)
(continued)
 239

Table B-2-a. (continued)

atom X y z
C(33) 0.7473(4) -0.0301(3) 0.0077(3) 1.64(7)
C(34) 0.8540(4) -0.0412(3) -0.0688(3) 2.36(9)
C(35) 0.8596(5) 0.0228(3) -0.1512(3) 3.0(1)
C(36) 0.7586(6) 0.0984(4) -0.1574(3) 3.7(1)
C(37) 0.6541(5) 0.1117(3) -0.0823(4) 3.2(1)
C(38) 0.6477(4) 0.0485(3) . 0.0021(3) 2.44(9)
C(39) 0.7183(3) 0.0311(2) 0.4860(2) 1.12(6)
C(40) 0.6320(3) 0.1252(3) 0.5007(3) 1.62(7)
C(41) 0.6417(4) 0.2044(3) 0.5494(3) 1.83(8)
C(42) 0.7399(4) 0.1913(3) 0.5816(3) 1.89(8)
C(43) 0.8271(4) 0.0987(3) 0.5663(3) 1.99(8)
C(44) 0.8170(3) 0.0178(3) 0.5185(3) 1.56(7)
C(45) 0.9928(4) -0.2383(3) 0.2765(4) 3.2(1)
C(46) 1.0115(4) -0.5789(4) 0.3124(4) 3.5(1)
C(47) 1.0232(4) -0.6752(4) 0.4616(4) 3.6(1)
C(48) 1.0378(6) -0.7651(5) 0.3164(5) 5.6(2)

Equivalent temperature factor:

Btq = -7t (U„(aa*) + U (bb*) + U (cc*)

2 2
22
2
3)
2
+ 2fJ12aa*bb*cosy + 2rj13aa*cc*cosp +

2fJ bb*cc*cosa)
23
 240

T abl
e B-2-b. Anisotropic displacement parameters for Zn(TPPBr )-(MeOH)-(DMF)
4

atom ^22 U33

U
n C7
13 u*
Br® 0.0403(2) 0.0150(2) 0.0120(2) -0.0079(2) -0.0010(2) -0.0041(1)
Br(2) 0.0444(2) 0.0194(2) 0.0130(2) -0.0126(2) 0.0061(2) -0.0009(1)
Br(3) 0.0841(4) 0.0252(2) 0.0243(2) -0.0213(2) -0.0284(2) -0.0013(2)
Br(4) 0.0524(3) 0.0255(2) 0.0177(2) -0.0111(2) -0.0198(2) 0.0036(2)
Zn® 0.0184(2) 0.0076(2) 0.0099(2) -0.0046(2) -0.0047(2) 0.0011(1)
O(l) 0.016(1) 0.018(1) 0.032(2) -0.004(1) -0.004(1) 0.004(1)
0(2) 0.039(2) 0.038(2) 0.102(3) -0.023(2) -0.046(2) 0.035(2)
N® 0.016(1) 0.009(1) 0.011(1) -0.004(1) -0.004(1) 0.002(1)
N(2) 0.016(1) 0.010(1) 0.012(1) -0.004(1) -0.004(1) 0.000(1)
N(3) 0.023(2) 0.010(1) 0.011(1) -0.007(1) -0.006(1) 0.000(1)
N(4) 0.020(1) 0.009(1) 0.009(1) -0.002(1) -0.005(1) 0.000(1)
N(5) 0.025(2) 0.030(2) 0.053(3) -0.003(2) -0.005(2) 0.010(2)
C(I) 0.015(2) 0.011(1) 0.013(2) -0.004(1) -0.005(1) -0.001(1)
C(2) 0.019(2) 0.011(1) 0.015(2) -0.007(1) -0.006(1) 0.001(1)
C(3) 0.016(2) 0.015(2) 0.012(2) -0.006(1) -0.001(1) 0.001(1)
C(4) 0.012(2) 0.012(1) 0.008(2) -0.003(1) -0.004(1) 0.003(1)
C(5) 0.014(2) 0.012(2) 0.015(2) -0.007(1) -0.008(1) 0.004(1)
C(6) 0.013(2) 0.009(1) 0.015(2) -0.004(1) -0.006(1) 0.002(1)
C(7) 0.019(2) 0.011(1) 0.018(2) -0.005(1) -0.006(1) 0.003(1)
C(8) 0.026(2) 0.008(1) 0.015(2) -0.004(1) -0.005(1) 0.000(1)
C(9) 0.015(2) 0.007(1) 0.015(2) -0.006(1) -0.004(1) 0.000(1)
C(10) 0.021(2) 0.012(2) 0.014(2) -0.006(1) -0.002(1) -0.004(1)
C(ll) 0.019(2) 0.014(2) 0.013(2) -0.007(1) -0.002(1) -0.004(1)
C(12) 0.030(2) 0.019(2) 0.015(2) -0.009(2) -0.007(2) -0.003(1)
C(13) 0.027(2) 0.020(2) 0.010(2) -0.008(2) -0.004(1) 0.001(1)
C(14) 0.019(2) 0.014(2) 0.008(2) -0.004(1) -0.002(1) 0.000(1)
C(15) 0.022(2) 0.011(2) 0.012(2) -0.002(1) -0.003(1) 0.001(1)
C(16) 0.023(2) 0.010(1) 0.013(2) -0.003(1) -0.004(1) 0.002(1)
C(17) 0.040(2) 0.012(2) 0.017(2) -0.008(2) -0.010(2) 0.005(1)
C(18) 0.032(2) 0.011(2) 0.016(2) -0.008(2) -0.007(2) 0.000(1)
C(19) 0.024(2) 0.008(1) 0.016(2) -0.005(1) -0.009(1) 0.000(1)
C(20) 0.017(2) 0.008(1) 0.015(2) -0.001(1) -0.006(1) -0.001(1)
C(21) 0.017(2) 0.008(1) 0.009(2) -0.001(1) -0.003(1) -0.001(1)
C(22) 0.019(2) 0.016(2) 0.018(2) -0.004(1) -0.009(1) 0.000(1)
C(23) 0.032(2) 0.020(2) 0.018(2) 0.002(2) -0.015(2) -0.002(1)
C(24) 0.038(2) 0.014(2) 0.007(2) -0.001(2) -0.003(2) 0.002(1)
C(25) 0.026(2) 0.014(2) 0.021(2) -0.008(2) -0.002(2) 0.004(1)
C(26) 0.017(2) 0.013(2) 0.018(2) -0.002(1) -0.008(1) -0.001(1)
C(27) 0.028(2) 0.010(1) 0.012(2) -0.006(2) -0.002(1) -0.001(1)
C(28) 0.037(2) 0.024(2) 0.019(2) -0.017(2) 0.007(2) -0.009(2)
C(29) 0.054(3) 0.027(2) 0.025(2) -0.026(2) 0.004(2) -0.009(2)
C(30) 0.071(3) 0.019(2) 0.021(2) -0.011(2) -0.001(2) -0.009(2)
C(31) 0.040(3) 0.028(2) 0.029(2) 0.004(2) 0.001(2) -0.012(2)
C(32) 0.029(2) 0.024(2) 0.022(2) -0.006(2) 0.000(2) -0.006(2)
(continued)
 241

Table B-2-b, (continues)

atom U n
rj 13 ^23
C(33) 0.043(2) 0.013(2) 0.008(2) -0.010(2) -0.009(2) 0.003(1)
C(34) 0.041(2) 0.026(2) 0.022(2) -0.011(2) -0.007(2) 0.000(2)
C(35) 0.067(3) 0.033(2) 0.016(2) -0.026(2) -0.003(2) 0.003(2)
C(36) 0.103(5) 0.028(2) 0.022(2) -0.028(3) -0.028(3) 0.012(2)
C(37) 0.069(3) 0.022(2) 0.032(3) -0.005(2) -0.029(3) 0.010(2)
C(38) 0.047(3) 0.021(2) 0.023(2) -0.003(2) -0.014(2) 0.002(2)
C(39) 0.022(2) 0.013(1) 0.010(2) -0.007(1) -0.004(1) 0.001(1)
C(40) 0.029(2) 0.015(2) 0.021(2) -0.008(2) -0.011(2) 0.001(1)
C(41) 0.036(2) 0.009(2) 0.023(2) -0.004(2) -0.009(2) -0.003(1)
C(42) 0.037(2) 0.019(2) 0.022(2) -0.015(2) -0.010(2) -0.004(1)
C(43) 0.027(2) 0.031(2) 0.025(2) -0.012(2) -0.013(2) -0.003(2)
C(44) 0.019(2) 0.019(2) 0.021(2) -0.002(2) -0.008(2) 0.000(1)
C(45) 0.031(2) 0.030(2) 0.067(4) -0.014(2) -0.018(2) 0.001(2)
C(46) 0.027(2) 0.049(3) 0.063(4) -0.017(2) -0.023(2) 0.027(3)
C(47) 0.035(3) 0.039(3) 0.056(3) -0.008(2) -0.014(2) 0.024(2)
C(48) 0.072(4) 0.049(3) 0.072(5) -0.006(3) -0.004(4) -0.010(3)

The general temperature factor expression:

e x p ^ T i ^ a * ^ / + b* U k
2 2 2
22
2
+ c* U /
2
3 + 2a*b*t/ M + 2a*c*rj /,/+ 2b*c*L7 /fe/
12 13 23
 242

Tabl
e B-3-a. Atomic coordinates and B„ for Zn(TPP(CH ) )-(THF) -(CHCl ),
3 4 16 3

atom X y z
Zn© 0.26812(5) 0.12829(4) 0.87154(5) 1.19(1)
CI© 0.1904(4) 0.0949(3) 0.3699(3) 6.7(1)
Cl(2) 0.2592(4) 0.2290(3) 0.4358(4) 5.2(1)
Cl(3) 0.3791(7) 0.1530(5) 0.3397(5) 8.0(2)
0(1) 0.2693(4) 0.2483(2) 0.8706(3) 2.6(1)
0(2) 0.2858(7) 0.0902(5) 0.3694(6) 4.4(2)
N© 0.2283(3) 0.1139(3) 0.7589(3) 1.3(1)
N(2) 0.1244(3) 0.1180(3) 0.8938(3) 1.1(1)
N(3) 0.3076(3) 0.1145(3) 0.9843(3) 1.2(1)
N(4) 0.4112(3) 0.1155(3) 0.8494(3) 1.2(1)
C© 0.2890(4) 0.1004(3) 0.7035(3) 1.1(1)
C(2) 0.2343(5) 0.0816(3) 0.6346(4) 1.3(1)
C(3) 0.1361(4) 0.0900(3) 0.6487(4) 1.3(1)
C(4) 0.1338(4) 0.1099(3) 0.7262(3) 1.2(1)
C(5) 0.0496(4) 0.1254(4) 0.7663(3) 1.2(1)
C(6) 0.0462(4) 0.1300(4) 0.8431(3) 1.3(1)
C(7) -0.0423(4) 0.1432(4) 0.8827(3) 1.5(1)
C(8) -0.0170(4) 0.1370(4) 0.9550(3) 1.5(1)
C(9) 0.0874(4) 0.1209(4) 0.9633(3) 1.3(1)
C(10) 0.1415(4) 0.1099(3) 1.0302(3) 1.3(1)
C(ll) 0.2443(4) 0.1001(3) 1.0393(3) 1.1(1)
C(12) 0.3009(5) 0.0792(3) 1.1077(4) 1.5(1)
C(13) 0.3983(4) 0.0868(3) 1.0936(3) 1.2(1)
C(14) 0.4021(4) 0.1093(3) 1.0166(3) 1.1(1)
C(15) 0.4875(4) 0.1221(3) 0.9763(3) 1.2(1)
C(16) 0.4898(4) 0.1239(4) 0.9004(3) 1.3(1)
C(17) 0.5789(4) 0.1321(4) 0.8613(3) 1.6(1)
C(18) 0.5542(4) 0.1272(4) 0.7875(3) 1.6(1)
C(19) 0.4468(4) 0.1167(4) 0.7801(3) 1.3(1)
C(20) 0.3938(4) 0.1069(3) 0.7125(3) 1.4(1)
C(21) 0.2714(5) 0.0547(4) 0.5623(4) 2.2(2)
C(22) 0.0455(5) 0.0720(4) 0.5890(4) 2.2(2)
C(23) 0.2626(5) 0.0461(4) 1.1761(4) 2.5(2)
C(24) 0.4834(5) 0.0682(4) 1.1484(4) 1.8(2)
C(25) -0.0471(4) 0.1397(4) 0.7222(4) 1.3(1)
C(26) -0.0647(5) 0.2056(4) 0.6863(4) 2.0(2)
C(27) -0.1513(5) 0.2175(4) 0.6438(4) 2.7(2)
C(28) -0.2223(5) 0.1636(4) 0.6392(4) 2.6(2)
C(29) -0.2081(5) 0.0976(4) 0.6766(4) 2.6(2)
C(30) -0.1208(5) 0.0857(4) 0.7183(4) 2.0(2)
C(31) 0.0832(4) 0.1127(3) 1.0982(3) 1.3(1)
C(32) 0.0164(4) 0.0577(4) 1.1144(4) 1.6(2)
C(33) -0.0348(4) 0.0621(4) 1.1801(4) 1.8(2)
C(34) -0.0198(5) 0.1210(5) 1.2279(4) 2.4(2)
(continued)
 Tabl
e B-3-a. (continued)
atom X y z
C(35) 0.0428(5) 0.1770(4) 1.2097(4) 2.3(2)
C(36) . 0.0942(4) 0.1731(4) 1.1463(4) 2.0(2)
C(37) 0.5829(4) 0.1344(4) 1.0205(3) 1.2(1)
C(38) 0.5990(4) 0.1982(4) 1.0577(4) 1.7(1)
C(39) 0.6882(5) 0.2116(4) 1.0990(4) 2.5(2)
C(40) 0.7608(4) 0.1581(4) 1.1019(4) 2.4(2)
C(41) 0.7452(5) 0.0937(4) 1.0639(4) 2.2(2)
C(42) 0.6576(4) 0.0812(4) 1.0220(4) 1.8(2)
C(43) 0.4534(4) 0.1069(3) 0.6453(3) 1.1(1)
C(44) 0.5153(4) 0.0479(4) 0.6294(4) 1.7(1)
C(45) 0.5665(4) 0.0476(4) 0.5668(4) 2.1(2)
C(46) 0.5632(5) 0.1059(5) 0.5197(4) 2.3(2)
C(47) 0.5047(5) 0.1660(4) 0.5340(4) 2.2(2)
C(48) 0.4504(4) 0.1663(4) 0.5973(4) 1.7(1)
C(49A) 0.3495(8) 0.2900(6) 0.9008(7) 0.6(2)
C(50) 0.3115(6) 0.3694(5) 0.9017(4) 3.6(2)
C(51) 0.2362(6) 0.3695(5) 0.8364(5) 3.7(2)
C(52A) 0.226(1) 0.292(1) 0.813(1) 3.8(4)
C(53) 0.166(1) 0.1741(9) 0.4080(8) 4.3(3)
C(54) 0.255(2) 0.220(1) 0.378(2) 8.6(5)
C(55) 0.320(2) 0.162(1) 0.360(1) 5.8(4)
C(56) 0.249(3) 0.185(2) 0.354(2) 7.5(6)
C(49B) 0.314(2) 0.288(2) 0.925(2) 7.5(6)
C(52B) 0.186(1) 0.2938(8) 0.8415(9) 2.4(3)

Equivalent temperature factor:

B = 3 7 i ( U „ ( a a * ) + U (bb*) + U (cc*) + 2L7 aa*bb*cosy + 2C7 aa*cc*cosP +

tq
2 2
22
2
33
2
12 13

,bb*cc*cosa)
 244

Tabl
e B-3-b. Anisotropic displacement parameters for Zn(TPP(CH ) )'(THF) /(CHCi ),
3 4 1 f 3

atom ^33 U u u„ u 23

Zn© 0.0077(3) 0.0205(4) 0.0171(4) 0.0000(4) 0.0008(2) -0.0007(5)

O(l) 0.031(2) 0.023(2) 0.042(3) 0.002(3) -0.012(2) -0.001(3)
N© 0.010(3) 0.022(3) 0.018(3) -0.004(2) 0.004(2) 0.003(2)
N(2) 0.009(2) 0.018(3) 0.014(3) -0.001(2) -0.002(2) -0.001(2)
N(3) 0.005(2) 0.016(3) 0.024(3) -0.001(2) 0.000(2) -0.001(2)
N(4) 0.016(3) 0.017(3) 0.013(3) -0.001(2) 0.000(2) -0.002(2)
C© 0.010(3) 0.019(4) 0.013(3) 0.002(2) 0.002(3) 0.002(3)
C(2) 0.013(3) 0.020(3) 0.018(4) 0.003(3) 0.000(2) -0.005(4)
C(3) 0.014(3) 0.017(4) 0.020(4) 0.001(3) -0.001(3) 0.003(3)
C(4) 0.011(3) 0.022(4) 0.013(3) -0.003(2) -0.003(3) 0.005(3)
C(5) 0.012(3) 0.013(3) 0.019(3) -0.005(3) -0.003(2) 0.004(3)
C(6) 0.014(3) 0.019(3) 0.017(3) -0.001(3) 0.000(2) -0.003(3)
C(7) 0.008(3) 0.028(4) 0.019(4) -0.001(3) -0.002(3) -0.003(3)
C(8) 0.008(3) 0.027(4) 0.024(4) -0.003(3) 0.007(2) 0.001(3)
C(9) 0.016(3) 0.016(4) 0.016(3) 0.002(3) 0.003(3) 0.001(3)
C(10) 0.011(3) 0.015(4) 0.023(4) -0.001(2) 0.005(3) 0.004(3)
C(ll) 0.012(3) 0.012(3) 0.019(4) 0.000(2) 0.003(3) 0.001(3)
C(12) 0.021(3) 0.021(4) 0.015(4) 0.000(3) 0.006(3) -0.001(3)
C(13) 0.016(3) 0.015(3) 0.016(4) -0.004(3) -0.001(3) -0.002(3)
C(14) 0.016(3) 0.013(4) 0.014(3) 0.002(2) -0.003(3) -0.005(3)
C(15) 0.010(3) 0.013(3) 0.024(4) 0.001(3) -0.001(3) 0.002(3)
C(16) 0.012(3) 0.018(3) 0.017(3) -0.002(3) -0.003(2) -0.004(3)
C(17) 0.007(3) 0.025(4) 0.028(4) -0.002(3) 0.000(3) -0.007(3)
C(18) 0.010(3) 0.032(4) 0.021(3) -0.002(3) 0.002(2) -0.005(4)
C(19) 0.008(3) 0.028(4) 0.016(3) 0.003(3) 0.004(2) 0.002(3)
C(20) 0.015(3) 0.021(4) 0.018(4) 0.004(3) -0.001(3) 0.001(3)
C(21) 0.019(4) 0.039(5) 0.026(4) 0.003(3) 0.005(3) 0.001(3)
C(22) 0.021(4) 0.024(4) 0.039(5) 0.008(3) 0.024(3) 0.004(3)
C(23) 0.024(4) 0.047(5) 0.026(4) 0.011(3) 0.007(3) 0.007(4)
C(24) 0.016(4) 0.019(4) 0.035(4) -0.001(3) 0.002(3) 0.010(3)
C(25) 0.009(3) 0.023(4) 0.017(4) 0.001(3) -0.002(3) 0.003(3)
C(26) 0.020(4) 0.023(4) 0.034(4) -0.003(3) -0.008(3) 0.004(3)
C(27) 0.035(4) 0.024(4) 0.040(5) 0.001(3) -0.017(3) 0.006(4)
C(28) 0.019(4) 0.036(5) 0.041(5) 0.006(3) -0.012(3) -0.004(4)
C(29) 0.017(4) 0.038(5) 0.044(5) -0.005(3) -0.004(3) 0.007(4)
C(30) 0.015(4) 0.028(4) 0.033(5) -0.004(3) -0.005(3) 0.015(4)
C(31) 0.008(3) 0.022(4) 0.020(4) 0.004(2) -0.001(3) 0.002(3)
C(32) 0.013(3) 0.023(4) 0.025(4) -0.002(3) 0.003(3) 0.002(3)
C(33) 0.014(3) 0.030(4) 0.024(4) 0.002(3) 0.004(3) 0.014(3)
C(34) 0.020(4) 0.047(5) 0.027(4) 0.006(3) 0.013(3) -0.004(4)
C(35) 0.030(4) 0.034(5) 0.023(4) 0.003(3) 0.001(3) -0.007(3)
C(36) 0.021(4) 0.025(4) 0.030(4) -0.003(3) 0.005(3) -0.007(3)
C(37) 0.006(3) 0.020(4) 0.019(3) .-0.004(3) 0.001(2) -0.002(3)
C(38) 0.017(3) 0.021(4) 0.026(4) 0.003(3) -0.001(3) -0.004(3)
(continued)
 245

Tabl
e B-3-b. (continued)
atom U u Un rj 12 L73
1
fj 23

C(39) 0.028(4) 0.023(4) 0.043(5) -0.006(3) -0.007(3) -0.006(4)

C(40) 0.011(3) 0.037(4) 0.040(5) -0.001(3) -0.014(3) -0.003(4)
C 0.019(4) 0.020(4) 0.044(5) 0.006(3) -0.011(3) -0.001(4)
(41
C(42) 0.021(4) 0.014(4) 0.033(4) 0.003(3) -0.006(3) -0.003(3)
C(43) 0.009(3) 0.021(4) 0.013(3) -0.001(2) 0.003(3) -0.001(3)
C(44) 0.019(3) 0.025(4) 0.019(4) 0.004(3) -0.002(3) -0.002(3)
C(45) 0.012(3) 0.038(5) 0.030(4) 0.002(3) 0.000(3) -0.007(4)
C(46) 0.017(4) 0.059(6) 0.012(4) -0.003(3) 0.007(3) -0.007(4)
C(47) 0.024(4) 0.037(5) 0.023(4) -0.011(3) 0.001(3) 0.015(4)
C(48) 0.017(3) 0.024(4) 0.023(4) 0.003(3) -0.001(3) -0.002(3)
C(50) 0.060(5) 0.025(4) 0.052(5) -0.008(4) 0.021(4) -0.006(5)
C(51) 0.047(5) 0.025(4) 0.071(6) 0.005(4) 0.012(4) 0.010(5)

The general temperature factor expression:

exr3(-2n\a* U h
z
u
2
+ b^U^k + c * r j / + 2a*b*U hk + 2a*c*l7<W + 2 b * c * f J £ /
2 2
33 n 1
3 23

Parameters:

a, b, c, a, (3, y; lattice constants (refer to Table 2-12)

a*, b*, c*; reciprocal lattice parameters ^ 2 8