Chalcogeno (S, Se or Te)-Substituted Compounds:

Designing and Applications in Organic Synthesis

and Material Science

DR. ARUN KUMAR

Department of Chemistry
Indian Institute of Technology
Delhi 1
 OUTLAY OF THE PRESENTATION
 Post Doctoral Research
 Palladium Chalcogenide Nanoparticles: Generation , Isolation and Applications

 Chalcogeno Substituted Liquid Crystalline Materials: Syntheses and Applications

 Se and Te Substituted Schiff Bases As Sensors: Syntheses and Application

 Ph.D. Research
 Introduction
 Chalcogenated Schiff Bases: Designing and Characterization
 Palladium Complexes: Designing, Characterization and Applications
 Platinum Complexes: Designing and Characterization
 Ruthenium Complexes: Designing and Characterization
 Mercurry Complexes: Designing and Characterization 2
 Tellurides and Ditellurides containing Schiff Base Functionality
 Post Doctoral Research Work

 Palladium Chalcogenide Nanoparticles:

Generation , Isolation and Applications

 Chalcogeno Substituted Liquid Crystalline Materials:

Syntheses and Applications

 Se and Te Substituted Schiff Bases As Sensors:

Designing and Applications

3
Palladium Chalcogenide Nanoparticles:
Generation , Isolation and Applications

4
 Introduction
Suzuki-Miyaura cross-coupling reaction: one of the most important
methods known for sp2―sp2 C−C coupling.
Palladium Catalyst
Ar X + (OH)2B Ar
K2CO3, DMF, H2O
Aryl Halide Phenyl Boronic Acid

 Generally believed that reaction is catalyzed by palladium(0) species.

Uncertainity related with catalytic nature of many Pd-complexes: whether

true catalytic species or pre-catalysts only.

Several reports regarding the potential of palladacycles for efficient

catalysis of various organic reactions including C−C coupling reaction.

Few reports on use of chalcogenated palladacycles as catalyst precursors

for Heck coupling.

5
 Use of homogeneous (metal complexes of huge number of ligands)
and heterogeneous catalysts (metal oxides, supported catalysts on
zeolites/silica /coal or polymer resins) for catalyzing various organic
reactions.
 Certain drawbacks of both approaches:
 Difficulty related with the separation of homogeneous catalysts from
reaction mixture so possibility of contamination of the product with
catalyst.
 A limitation of lower activity and deactivation of the catalyst in case
of heterogeneous reactions.
 A solution for lower activities of heterogeneous catalysts: catalysis by
nanoparticles (Nano-Catalysis) due to their large surface area.
 Taking into account:
 The high catalytic activities and air/moisture insensitivity of
palladium-complexes of chalcogeno substituted (S, Se or Te)−
compounds
 Large number of other applications of nanoparticles.
 It was thought worthwhile to synthesize the nanoparticles of
6
Palladium−Chalcogenides and to explore their application in catalysis.
 Palladium Selenide Nanoparticles:
Generation and Isolation

NaBH4
N Se N Se
EtOH H
OH OH
Imine
Secondary Amine

Na2PdCl4
CH3-CO-CH3/H2O
Pd17Se15
Nanoparticles Cl
Pd
NH Se
OH
Chem. Commun., 2010, 46, 5954
Se Ligated Palladacycle

Ar Ar X + (OH)2B
K2CO3, DMF, H2O
Aryl Halide
Phenyl Boronic Acid
7

Suzuki-Miyaura C - C Coupling Reacion

 Single Crystal Structure of Se Ligated Palladacycle

Geomery
around Pd:

Square Planar

Selected bond lengths (Å) Selected bond angles (°):

C(18)−Pd(1)−N(1) 82.00(19);
Pd(1)—C(18) 1.973(5); C(18)−Pd(1)−Cl(1) 94.93(16);
Pd(1)—N(1) 2.056(4); N(1)−Pd(1)−Se(1) 97.62(12);
Pd(1)—Cl(1) 2.325(16); Cl(1)−Pd(1)−Se(1) 85.61(6); 8
Pd(1)—Se(1) 2.528(11). Chem. Commun., 2010, 46, 5954
 Charaterizaion

5000 Acquire EDX

Size: ~10 nm
Cu
4000

3000

Counts
2000 Pd
Pd

Se
C Se

Se
1000 Pd
Pd Pd
Cu Cu
Se
Cu
Cu
Se
Si Pd
O Pd Se
Si Pd
0
0 5 10 15
Energy (keV)

HRTEM Image EDX

of Pd17Se15 after Annealing at 450 ºC

9

Chem. Commun., 2010, 46, 5954

 Powder XRD Pattern of Pd17Se15.

The pattern has been indexed and peaks with the following observed d (Å) values
(hkl): 3.32 (310), 3.17 (311), 2.92 (320), 2.81 (321), 2.56 (410), 2.49 (411), 2.42
(311), 2.36 (420), 2.30 (430), 2.11 (431), 2.06 (511), 2.03 (440), 1.86 (433), 1.76
10
(600), 1.71 (532), 1.65 (540), 1.63 (541)
Chem. Commun., 2010, 46, 5954
Palladium Sulfide and Palladium Telluride Nanoparticles: Generation and Isolation

Palladium Sulfide
Cl
Nanoparticles Pd
NH S
OH
S Ligated Palladacycle

Ar
K2CO3, DMF, H2O
Ar X
+ (OH)2B
Aryl Halide
Phenyl Boronic Acid

Cl OMe
Pd
K2CO3, DMF, H2O NH Te
OH
Te Ligated Palladacycle

Palladium Telluride
11
Ar Nanoparticles
Characterization of Palladium Telluride Nanoparticles

HRTEM image and EDX of PdxTey

12
Characterization of Palladium Sulfide Nanoparticles

HRTEM Image of PdxSy

13
 Applicaion of Palladium Sulfide, Palladium Selenide
and Palladium Telluride Nanoparticles

(1)Application in Nano Catalyis:

Nano sized particles of palladium chalcogenides have been explored as
highly efficient catalysts in Suzuki Miyaura C−C Coupling reactions. The thermal
stability, aerobic and moisture insensitivity are additional advantages of these nano-
particles in the area of catalysis.

(2)Magnetic Properies:
These properties are currently under the process of investigation and will be
reported soon.

14
 Chalcogeno Substituted
Liquid Crystalline Materials:
Syntheses and Applications

15
 Se Substituted Liquid Crystalline Materials:

•Seleno substituted Schiff bases showing Liquid Crystalline Properties

C10H21
O
O
N
C18H37 O
O N
O OH O OH
Se Se

1 2

C10H21 O
O
C10H21 O N
O OH
C10H21 O Se
3

•Telluriun and Sulfur analogues of these compound have also been

16
explored as liquid crystalline materials.
 Characterization by Polarized Optical Microscopy (POM)

Alkyl Chain: —C10H21

A (43.9 ºC) B (46.0 ºC)

17

C(65.6°C) Polarized Optical Micrographs D(66.0 ºC)

 Alkyl Chain: C18H37

A (68.6 ºC) B (72.7 ºC)

B (97.5 ºC) C (98.5 ºC) 18

Polarized Optical Micrographs

 Palladium Complexes of Liquid Crystalline Compounds

C10H21 O
O N Na2PdCl4
C10H21 O
O OH O N
Se O O Pd
Cl Se

C10H21
C18H37
O
O O
O N C10H21 O N
O O Pd O O Pd
Cl Se C10H21 O Cl Se

•Telluriun and Sulfur analogues of these compound have also been

synthesized.
19
•Absence of liquid crystalline properties in all of them.
 Effect of Liquid Crystalline Properties of Compounds
On Nanoparticles of their Palladium Complexes

C10H21 O
O
O O Pd
N
C18H37 O
Cl Se O N
Aggregated Nanoparticles O O Pd

Composition: Mono Dispersed Cl Se

Se: 45% Composition:

20
Pd: 55% Se: 60%
Pd: 40%
 Scope of the Work and Conclusion

 Great interest in the synthesis of noble metal nanoparticles for

many decades because of their use in applications such as catalysis,
photonics, electronics, and biomedical sensing.

 Dependence of these intriguing properties strongly on the size and

shape of the nano-particles.

 An important subject of chemical research: controlled synthesis of

nanoparticles with well-defined shape and size.

 Many Reports related with the development of synthetic methods

by varying the reaction conditions.

 First report: on the influence of lengths of alkyl chains (present

on precursor’s framework) on Size, Dispersion and
Composition of nanoparticles.
 Possibility of using these results as a new basis for controlled
21
synthesis of nanoparticles.
Se and Te Substituted Schiff Bases
as Sensors:
Designing and Applications

22
 Se
N Schiff Bases substituted with Se have been
OH designed and explored as sensor for Pd(0)
OH
The color transition is readily visible to the
N
Se naked eye as a yellow to red color change.

Te Schiff base substituted with Te have been

N
designed and explored as sensor for Hg(II).
OH OMe
OH OMe

N
Te

23
 Ph.D. Research Work
 Introduction
 Chalcogenated Schiff Bases: Designing and Characterization
 Palladium Complexes: Designing, Characterization and
Applications
 Platinum Complexes: Designing and Characterization
 Ruthenium Complexes: Designing and Characterization
 Mercurry Complexes: Designing and Characterization
 Tellurides and Ditellurides containing Schiff Base Functionality

24
Compounds containing S, Se or Te are very much attracive for designing
new catalysts because of strong ligating properties of chalcogen atoms.

Organoselenides, when used as ligands in catalytically active species, offer

great potential in transition metal-catalyzed C−C bond forming reactions such
as the palladium-mediated Heck reaction. These catalysts not only rival but, in
most cases, outperform each of their respective phosphorus and sulfur
analogues for similar Heck reactions of aryl bromides

Org. Lett., 2004, 6, 2997 25

Interest in Te and Se ligands has grown in last decade due to availability of
standardized synthetic routes and FT−NMR for studying solution behavior.

Hybrid ligands containing S, Se and Te can be easily designed by

chalcogenating Schiff base framework.

Schiff bases are important ligands as their metal complexes can show a
variety of catalytic organic reactions.

No detailed comparative study on chalcogenated Schiff bases of mono ketones

or aldehydes has been made

Possibility of significant modification in the known catalytic roles of Schiff

bases by the presence of S, Se or Te as a donor site in them . Therefore, such
systems are worth exploring.

Phosphine based catalysts are often water–and air–sensitive. Therefore,

catalysis under phosphine–free conditions is a challenge of high importance, and
Pd–complexes of phosphine–free ligands which have promising catalytic activity
for C—C coupling reactions are of current interest.

The chalcogenated Schiff bases may deal with this challenge in a better way
because the chalcogen based catalysts are air stable and also not moisture
26

sensitive.
 Objectives
Design chalcogenated Schiff base ligands containing S, Se or Te donor sites
along with N and O.

Explore the coordination chemistry of the newly designed ligands with ‘Soft/
Hard’ metallic and organometallic species.

Study the use of Pd(II) complexes in organic synthesis (catalytic C—C coupling
reactions).

27
 Chalcogenated Schiff Bases:
Designing and Characterization

28
 Chalcogenated Schiff Bases Explored

E R
Me Me
N N E R E:
OH OH

S
E R
Me Me or
N N E R

OH OH

Se
E R or

N N E R

OH OH
Te
29

N—(CH2)2—E system N—(CH2)3—E system

 Precursors Used in The Syntheses
Methodology of Syntheses: Amine + Keone → Schiff Base + Water

Me
O

OH
NH2 S H2N S

Me
O

OH
NH2 Se H2N Se

NH2 Te OMe H2N Te OMe

O

OH

30
Chalcogenated Amines
Keones
Characteization Methods of Schiff Bases

 C, H, N Analyses
 IR Spectrocopy
 1
H NMR Spectrocopy
 13
C{1H} NMR Spectroscopy
 77
Se{1H} NMR Spectroscopy
 125
Te{1H} NMR Spectroscopy
 Single Crystal X-Ray Diffraction

31
 Tellurated Schiff Base Te{1H) NMR
125

OMe
CH3 δ 460.3 ppm
N Te
125
Te{1H} NMR signal :

OH Appears at a position similar to that of

corresponding free amine

Crystal system Triclinic

Space group P−1
a 6.3152(5) Å
b 8.7203(7) Å
c 18.3132(14) Å
α 85.6160(10) °
β 85.8362(11) °
γ 76.6560(10) °

Te(1)—C(16) 2.116(2) Å
Te(1)—C(15) 2.160(3) Å
N(1)······H(1) 1.770(2) Å

C(15)—Te(1)—C(16) 95.15(9)°
32
C(11)—N(1)—C(13) 124.5(2)°
 Selenated Schiff Base

CH3

N Se

OH

77
Se{1H) NMR δ 286.6 ppm

Crystal system Monoclinic Se(1)—C(12) 1.914(3) Å

Space group P2(1)/c Se(1)—C(11) 1.956(3) Å
a 16.474(3) Å N(1)·∙∙··H 1.53(6) Å
b 6.7098(11) Å
c 14.689(2) Å C(11)—Se(1)—C(12) 99.5(1)°
β 108.084(2) ° C(7) )—N(1) )—C(9) 122.0(2)°

33
 Sulphated Schiff Base

S
N
Crystal System Monoclinic
Space group P2(1)/c OH
a 6.7921(16)Å
b 18.802(5) Å
c 13.883(3) Å
β 91.077(4)°

S—C(Aryl) is shorter than S—C(Alkyl)

S—C(16) 1.764(4) Å
S—C(15) 1.833(4) Å
N···H 1.793(3) Å

C(16)—S—C(15) 105.39(18)°
C(1)—N—C(14) 121.4(3)°
34
 Special NMR Spectral Features of Tellurated Schiff Bases
Me OMe
Te Me
N
N Te
OH OMe
OH
L11
L12
N—(CH2)2—Te system N—(CH2)3—Te system

OMe
1
Te
N N Te
OH OMe
OH
L13 L14

Deshielded by 52−72 ppm Te{1H}

125 Remains almost unchanged.
(wth respect to that of ArTe(CH2)2NH2) NMR signal

Shielded by 6−8 ppm TeCH2 Remains almost unchanged

(with respect to that of Ar Te(CH2)2NH2) carbon signal 35
 Palladium Complexes:
Designing, Characterization and Applications

36
 Molecular Structure of Palladium Complexes

Me Me
N E R N E R E:
Pd Pd

O Cl O Cl
S

or

N—(CH2)3—E system N—(CH2)2—E system

Both the rings are One ring is 5 membered Se
Six membered. Other ring is 6 membered
or

Te

37
 General Methodology for the Syntheses

Me Me
Na2PdCl4
N E R N E R
Acetone/Water, Room Temp. Pd
OH O Cl

Characteization Methods

 C, H, N Analyses
 IR Spectrocopy
 1
H NMR Spectrocopy
 13
C{1H} NMR Spectroscopy
 77
Se{1H} NMR Spectroscopy
 125
Te{1H} NMR Spectroscopy
 Single Crystal X-Ray Diffraction 38
 Crystal Structure of Palladium Complex of 125
Te{1H) NMR

H3C
Te Schiff Base δ 764.1 ppm

N Te OMe 125
Te{1H} NMR signal :
Pd
O Cl
Deshielded by 298 ppm with
respect to that of
Schiff base
Crystal system Orthorhombic
Space group C2cb
a 9.7664(3) Å
b 16.1747(6) Å
c 27.8791(9) Å

Pd(1)—Te(1) 2.5025(7) Å
Pd(1)—Cl(1) 2.293(2) Å
Pd(1)—N(1) 1.996(7) Å
Pd(1)—O(1) 2.061 (6) Å

N(1)—Pd(1)—Te(1) 89.2(2)°
Cl(1)—Pd(1)—Te(1) 88.30(6)°
N(1)—Pd(1)—O(1) 90.0(2)° 39
Cl(1)—Pd(1)—O(1) 92.59(16)°
 Crystal Structure of Palladium Complex of
Se Schiff Base

77
Se{1H) NMR δ 273.73 ppm
Crystal system Triclinic N Se (Shielded by 16.17 ppm in
Pd
Space group P−1 O Cl comparison to free ligand)
a 11.917(9) Å
b 12.161(8) Å
c 15.542(11) Å
α 89.004(13) °
β 84.589(14) °
γ 62.430(12) °

Pd(1)—Se(1) 2.392(2) Å
Pd(1)—Cl(1) 2.268(3) Å
Pd(1)—N(1) 1.979(6) Å
Pd(1)—O(1) 1.987(6) Å

N(1)—Pd(1)—Se(1) 94.30(19)°
Cl(1)—Pd(1)—Se(1) 86.57(7)°
N(1)—Pd(1)—O(1) 88.4(3)°
Cl(1)—Pd(1)—O(1) 90.83(18)°
40

 Square planar geometry at Pd (II)

 Crystal Structure of Palladium Complex of
S Schiff Base

H3C
N S
Pd
Crystal System Monoclinic O Cl
Space group P 2 (1)/c
a 16.038(9) Å
b 10.536(6) Å
c 12.351(7) Å
β 110.369(11)°

Pd(1)―S(1) 2.266(4) Å
Pd(1)―Cl(1) 2.309(4) Å
Pd(1)―N(1) 2.015(10) Å
Pd(1)―O(1) 1.998(8) Å

N(1)—Pd(1)—S(1) 97.5(3)°
Cl(1)—Pd(1)—S(1) 85.67(14)°
N(1)—Pd(1)—O(1) 87.5(4)°
Cl(1)—Pd(1)—O(1) 89.3(2)°
41

 Square planar geometry at Pd (II)

 Special NMR Spectral Features of Palladium(II) complexes:
 Disappearance of signal of OH proton in 1H NMR spectra.

N E N E
Pd Pd

O Cl O Cl

Both the rings are One ring is 5 membered

Six membered. Other ring is 6 membered
(N—(CH2)3—E) (N—(CH2)2—Esystem)

Deshielded between 298 and Magnitude of Deshielding is

308 ppm
Te{1H}
125
between 11 and 24 ppm
NMR
E:
Te signal E:
Te
Deshielded by ~150 pm
77
Se{1H} Deshielding is of only 7−11 ppm
NMR
E: Se Signal
E: Se 42
Change in signals of NCH2 and CH2S protons on Complexation

NCH2 CH2S
N SPh

OH

CH2S

N SPh
Pd
O
Cl

NCH2

43
 Application of Palladium Complxes
C—C Coupling Reaction:
Suzuki Reaction E : Te
Palladium Complex
R Br + (OH)2B R
K2CO3, DMF / H2O, 24 h at 100°C

Reaction Conditions:
Catalyst
Substituents on 23 31 Ar―Br = 1.0 mmol
Reactantants Ph—B(OH)2 = 1.5 mmol
Conversion (%)
(R) K2CO3 = 2 mmol
DMF = 4 mL
H2O = 0.5 mL
Catalyst = 0.001 mmol
OMe 10 10 Time = 24 h at 100°C
H 40 35

NO2 75 80 Conversion (%) is marginally lower

in comparision to the case of Pd(II)
complexes of selenated Schiff bases
44
at similar reaction conditions
 Heck Reaction
Palladium Complex Ar
Ar X +
Y Na2CO3, DMF, N2 atm, 24 h at 100°C
Y

Ar-X Y
23 31
Conversion (%)
E : Te
O2N I COOH 75 70 Reaction Conditions:

Ar―I = 1.0 mmol

Alkene = 1.5 mmol
Cl I COOH 65 60
Na2CO3 = 2 mmol
DMF = 4 mL
O2N Br COOH 32 30 Catalyst = 0.001 mmol
Time = 24 h at 100°C, N2 atm

O2N I Ph 75 72

Conversion (%) is marginally lower

Cl I Ph 75 70 in comparision to the case of Pd(II)
complexes of selenated Schiff bases
at similar reaction conditions
O2N Br Ph 32 35 45
 E : Se
Suzuki Reaction

Palladium Complex
R Br + (OH)2B R
K2CO3, DMF / H2O, 24 h at 100°C

Reaction Conditions:
Catalyst
Substituents on Ar―Br = 1.0 mmol
15 17 19 21 Ph—B(OH)2 = 1.5 mmol
Reactantants
Conversion (%) K2CO3 = 2 mmol
(R)
DMF = 4 mL
H2O = 0.5 mL
Catalyst = 0.001 mmol
15 10 20 15
Time = 24 h at 100°C
OMe
H 40 25 45 30 Conversion (%) is generally higher
85 82 87 84
in comparision to the case of Pd(II)
NO2
complexes of sulphated Schiff bases
46
at similar reaction conditions
 E : Se Palladium Complex
Heck Reaction
Ar
Ar X +
Y Na2CO3, DMF, N2 atm, 24 h at 100°C
Y
15 17 19 21
Ar-X Y Reaction Conditions:
Conversion (%)
Ar―I = 1.0 mmol
O2N I COOH 80 72 85 74 Alkene = 1.5 mmol
+ Na2CO3 = 2 mmol
DMF = 4 mL
Cl I COOH 74 68 80 65
Catalyst = 0.001 mmol
Time = 24 h at 100°C, N2 atm
O2N Br COOH 38 30 35 33

O2N I Ph 78 70 83 78 Conversion (%) is generally higher

in comparision to the case of Pd(II)
complexes of sulphated Schiff bases
Cl I Ph 70 65 78 68 at similar reaction conditions

O2N Br Ph 35 30 33 30 47
Suzuki Reaction

: S
E

Complex 7 / 8 / 9
R Br + (OH)2B R
K2CO3, DMF / H2O, 24h at 100°C

Substituents on Conversion (%)

Reactantant Reaction Conditions:
(R) 7 8 9
Ar―Br = 1.0 mmol
Ph—B(OH)2 = 1.5 mmol
25 10 30 K2CO3 = 2 mmol
OMe
DMF = 4 mL
45 20 50 H2O = 0.5 mL
H
Catalyst = 0.001 mmol
80 70 80 Time = 24 h at 100°C
NO2
48
 Application in Heck Reaction
Palladium Complex Ar
Ar X +
Y Na2CO3, DMF, N2 atm, 24 h at 100°C
Y
Catalyst
Ar-X Y 7 8 9
Conversion (%)
E: S
O2N I COOH 78 68 78

Cl I COOH 70 65 70
Reaction Conditions:

O2N Br COOH 35 25 25 Ar―I = 1.0 mmol

Alkene = 1.5 mmol
Na2CO3 = 2 mmol
O2N I Ph 75 68 74
DMF = 4 mL
Catalyst = 0.001 mmol
Time = 24 h at 100°C, N2 atm
Cl I Ph 78 60 70

49
O2N Br Ph 30 32 28
 Platinum Complexes:
Designing and Characterization

50
 Molecular Structure of Platinum Complexes in
N—(CH2)2—E System
Me
E:
N E R
Pd

O Cl S
One ring is 5 membered
or
Other ring is 6 membered

N—(CH2)2—E system
Se
General Methodology for the Syntheses or

Te
Me Me
K2PtCl4
N E R N E R
Acetone/Water, Room Temp. Pt
OH O Cl

51
 Molecular Structure of Platinum Complexes in
N—(CH2)3—E System

CH3 E:
N E
Cl
OH Trans Isomer
Pt
HO Se
Cl E N
or
CH3

Te
CH3
N E
E Cis Isomer
HO
OH N
Pt H3C

Cl
Cl
52
Ruthenium Complexes:
Designing and Characterization

53
Methodology of Syntheses of Ru(II) complexes:

Cl
Cl

Ru Ru
OMe
CH3 Cl
Cl
N Te

OH
Dichloromethane, RT

CH3
Cl
H3C
CH3
Ru
Te
H3C N
OMe
HO
 Characterization of Ru(II) complexes:
25 / 29: R = CH3, R’ & R’’ = −(CH2)4− Coordination Deshielding (49−75 ppm) of
33 / 37: R = Ph, R’ & R’’ = H through 125
Te{1H} NMR signal
Deshielding (10–11 ppm) of
CH3
Te C5 (CH2Te) Signal
Cl
H3C Deshielding (6–7 ppm)
and of C4 signal
CH3
Ru

CH R
3
or C 1
N
4 Te 4
N Shielding (~3ppm) of
OMe =NCH2 signal
HO 9 (CH2) Cl− Not through C9 carbon
C signal is Unchanged
n
OH signal is present in
n = 1 or 2 O 1
HNMR spectra.
R'
R'' Further Support: Change in signals of TeCH2 and
NCH2 protons after complexation
HRMS: (25) 720.0462 (M+−Cl) Ligand L13
(29) 734.0619 (M+−Cl) NCH2 TeCH2
Ru(II)
(33) 733.0520 (MH+−Cl) complex
Te
(37) 746.0614 (M+−Cl) N

OH OMe
55
Metal : Ligand Ratio 1:1
 Ru(II) Complex
CH3
Te TeCH2 NCH2 TeCH2
N
OH NCH2
OMe
L11

Ru(II) Complex
TeCH2

CH3 OMe =NCH2

NCH2 TeCH2 CH of
N Te i-pr
OH
L12

Ru(II) Complex
=NCH2 TeCH2
NCH2 + TeCH2
OMe
TeCH2 +
N Te CH of i-pr
OH
L14
56
 Mecurry Complexes:
Designing and Characterization

57
 Hg(II) complexes:
Shielding (85−105 ppm) of
26 / 30: R = CH3, R’ & R’’ = −(CH2)4− Coordination 125
Te{1H} NMR signal
34 / 38: R = Ph, R’ & R’’ = H through
Deshielding (11–14 ppm) of
R''
R' Te C5 (CH2Te) Signal
Deshielding (1.5–2.5 ppm)
HO Not through
9 of C4 signal
N CH or C 14) N =NCH2 : Unchanged
R (
3
and CH3 signal : Unchanged (in 26 and 30)
C14 signal : Unchanged (in 34 and 38)
(CH2)n
MeO 1
4
Te n = 2 or 3
O C9 signal
OH signal
: Unchanged
: Present in 1HNMR spectra.
3 Ligand L11 Hg(II) Complex δ 3.50
2
Hg δ 3.00 =NCH2 TeCH2
4
TeCH2
OMe
Br Te
Br
H 3C
N Te OMe

=NCH2 OH

(CH2)n
)
or C 14 R
(CH 3 N n = 2 or 3
Hg(II) Complex
OH L12 δ 2.88
9 =NCH2 TeCH2 NCH2 TeCH2
R''
δ 3.28
R' H3 C
N Te OMe

HRMS: (26) 1179.0170 (M −Br) + OH

(30) 1207.0450 (M+−Br) 58

Metal : Ligand Ratio 1:2

Ligand L13 δ 2.95 Hg(II) Complex
=NCH2 TeCH2
δ 3.49
=NCH2 TeCH2
Te
N

OH OMe

Ligand L14 Hg(II) Complex

δ 2.83 ppm
=NCH2 TeCH2
=NCH2
OMe

N Te δ 3.22 ppm
OH
TeCH2

59
 Tellurides and Ditellurides
containing Schiff base functionality

60
 Syntheses of Ditellurides containing Schiff base functionality
and their mono telluride analogues

CH3 CH3 CH3 CH3 CH3

Te H2N Te NH2 H2N Te Te NH2 Te Te
N N O N N
Dry MeOH, r.t. Dry MeOH, r.t.
OH (1) HO OH OH
(2) HO

CH3 CH3 CH3 CH3

Te CH3 Te Te
N N N N
H2N Te NH2 O H2 N Te Te NH2
OH OH
(3) HO
Dry MeOH, r.t. OH Dry MeOH, r.t.
(4)
HO

Te H2N Te NH2 H2N Te Te NH2 Te Te

N N N N
Dry MeOH, r.t. Dry MeOH, r.t.
O
OH (5) HO
OH
OH (6) HO

Corresponding Novel Ditellurides containing

Mono-telluride analogues Schiff base functionalty

Characterization of 1 to 6 has been carried out by

proton, carbon–13 and tellurium–125 NMR spectroscopy
61
 NMR Spectra of Ditelluride 2 & corresponding telluride 1
1 2 1 2
H3C CH3 H3C CH3
3 N Te N 3 N Te Te N
9 4 9 4
8 OH HO 8 OH HO
5 5 (2)
7 6 (1)
7 6

Corresponding Monotelluride containing First Example of Ditelluride containing

same Schiff Base Functionality Schiff Base Functionality

125
Te{1H} NMR δ 220.84 ppm δ 97.97 ppm
The 1H and 13C{1H} NMR spectra of 1 and 2 are almost similar except the position of
TeCH2 protons in 1HNMR spectra.
TeCH2 signal in 1HNMR δ 3.04 ppm δ 3.36 ppm

1 2
CH3 8
9
7
6 1 CH3
5 2
OH 7
6 9
8 3
4

62

1
H NMR Spectrum of 2 13
C{1H} NMR Spectrum of 2
 Significance of Ditellurides containing Schiff base functionality

The borohydride reduction of such compounds can generate first

examples of (N, O, Te−) ligands, which can be reacted further with
a variety of functionalized organic halides to prepare diverse
multidentate hybrid organotellurium ligands.
R
R R NaBH4 / NaOH (CH2)n
N TeNa
Dry C2H5OH, Reflux H
N (CH2)n Te Te (CH2)n N
OH OH
HO
First Example of intermediate
containing (O, N, Te) donor sites

Chloro compound
in C2H5OH

New Organotellurium Ligand

Thus importance of such compounds as precursors in the

context of furtherance of ligand chemistry of tellurium is
immense.
63
 Ligand Exchange Reaction of (2)
CH3 δ 98.0 ppm CH3 δ 457.0 ppm
Te Te Te Te
N N
+
OH (2) HO MeO (2a) OMe

Mixing of 2 with 2a in equimolar ratio in

CDCl3 leads to the formation of an asymmetric
ditelluride (2b). CH3
Te Te
N

OH (2b) OMe
Spectra are the sum of the contributions from each component of the
equilibrium mixture. OMe δ 14.63
δ 455.35 δ 287.7 δ 251.8 δ 97.97 14.76
CH3

2b
2a 2 δ 52.34 δ 3.47
52.44 4.54
NCH2 TeCH2

Te{1H} NMR Spectrum of

125
DEPT 135 NMR Spectrum of 64
Equilibrium Mixture of (2), (2a) and (2b) Equilibrium Mixture of (2), (2a) and (2b)
 Conclusion
Novel ditellurides containing Schiff base functionality have been designed for the first
time and their ligand exchange reactions with other ditellurides have been explored.

Monotellurides containing Schiff base functionality have been designed and compared
with ditellurides containing the same functionality.

Sulphated, Selenated and Tellurated Schiff bases (total 14 in number) have been
designed and their complexation with Pd(II), Pt(II), Ru(II) and Hg(II) has been carried out.

The complexation of selenated and tellurated Schiff bases with Pt(II) becomes different
when value of ‘n’ in the ligand backbone >C=N−(CH2)n−E changes from 2 to 3.

In 77Se{1H} and 125Te{1H} NMR spectra of Pd (II) / Pt(II) complexes, the shift of signal
relative to free ligand depends on the size of chelate ring (5-membered > 6 membered)

Study on the catalytic activity of Pd (II) complexes of (O, N, E)–Schiff base ligands for C
—C coupling reactions (Suzuki and Heck Type) has been made. The advantage of using
them is that they are air stable and also not moisture sensitive.

The catalytic activity of Pd (II) complexes of tellurated ligand in C—C coupling

reactions (Suzuki and Heck Type) has been explored first time.
 List of Publications
In Journals
Arun Kumar, Ajai K. Singh, “First ditelluride containing Schiff base functionality: synthesis and instantaneous ligand
exchange with other ditelluride investigated by 125Te NMR” Inorg. Chem. Commun.  10 (2007) 1315.

Arun Kumar, Monika Agarwal and Ajai K Singh, “Selenated Schiff bases of 2–hydroxyacetophenone and their
palladium(II) and platinum(II) complexes: syntheses and crystal structures and applications in Heck reaction”
Polyhedron 27(2008) 485.

Arun Kumar, Monika Agarwal, Ajai K. Singh, “Schiff bases of 1’–hydroxy–2’–acetonaphthone containing chalcogen
functionalities and their complexes with and (p–cymene)Ru(II), Pd(II), Pt(II) and Hg(II) : synthesis, structures and
applications in C─C coupling reactions” J. Organomet. Chem. (Accepted).

Arun Kumar, Monika Agarwal, Ajai K. Singh, “Palladium(II), platinum(II), ruthenium(II) and mercury(II) complexes
of potentially tridentate Schiff base ligands of (E, N, O) type (E = S, Se, Te): Synthesis, crystal structures and
applications in Heck and Suzuki C─C coupling reactions” Inorg. Chim. Act. (Under Review).

In Conferences / Symposia
 Arun Kumar, Ajai K. Singh, “Secondary interactions in crystals water soluble derivatives of tellurated alkylamines,
tellurated Schiff bases and metal complexes of hybrid organotellurium ligands”, 11th Symposium on Modern Trends in
Inorganic Chemistry (MTIC−XI), held at IIT Delhi, Dec 08-10, 2005.

Arun Kumar, Raghavendra Kumar P., Ajai K. Singh, “Multidentate organsulphur and organotellurium ligands and their
metal complexes: synthesis and structural aspects”, OMCA 07 National Symposium on Recent Trends in
Organometallic Compounds and Their Industrial Applications, held at KIIT University Bhubaneswar, Orissa, Feb
26−28, 2007.

Arun Kumar, Ajai K. Singh, “Polydentate tellurium and selenium ligands and their metal complexes: synthesis and
structural aspects”, 12th Symposium on Modern Trends in Inorganic Chemistry (MTIC−XI), held at IIT Chennai, Dec
06−08, 2007.
66
Thank you for
your
listening!!!
67
 Ring Opening Polymerization

O
O
O O Catalyst
O CH2.CH2.CH2.OC
n

Macromolecules 38 (2005) 5406

Asymmetric Enantoselective Conjugate Addition

to α, β−unsaturated imide

Nu O
O NuH
R R'
R R' (S, S)-[(salen)Al]2O

NuH = HN3, HCN, HSAr, R"CH2NO2, N N

Al
Bu-t O O t-Bu

t-Bu Bu-t
68

(S, S)-(salen)Al
 Selective Organic Transformations

HO

(R)−[CoII(L)] H
+ O2 L=
N N

ee: 38.0 % OH HO
Hydroxylation of Styrene

O OMe (R)−[TiIV(L)(OPri)2 OH O L=
+
R H Me 2N HCl R Me N HO
ee: 66-98 %
OH
Aldol Condensation 69
Br
 (S)−[MnII(L)] O
+ NaClO L=
N N
ee: 13−15 %
Epoxidation of Alkenes OH HO

Dehydrogenation plus intramolecular Diels–Alder cycloaddition

PPh3
N N
Ru
O2N O O NO2
PPh3 O
O NO2 O2N O
OH
O N N
H
O 70
 Multi–electron Redox Catalysis

Oxovanadium acetylacetonate
[ VO(acac)2 ]
+
2 SR S SR
−2e , −H − +
R

Oxidative Coupling of Aryl Sulfides

R
J. Org. Chem.
61 (1996) 1912
[VV] S

R
O2
[V ]III +
S S + H+
R

[ VO(salen-(NO2)2)], O2
S S S
CF3SO3H, CH2Cl2
n
R R
Electrophilic Substitution Reaction of sulfonium cations
formed bt the multi-electron oxidation of aromatic disulfide 71
 Kharasch Addition and Enol Ester Synthesis

R
N
Cl
Ru
O

R' R'Cl

R
+ CXCl3
R CXCl2
[X = Cl] R = Me or t-Bu
Atom Transfer Radical Addition (or Kharasch Addition)

R'
R R O
OH
+ R O
R' + R O
+ R' H
O O R' O O

Markovnikov anti-Markovnikov [E] anti-Markovnikov [Z]

Enol Ester Synthesis

72
 Alkene Polymerisation
(Ring–Opening Metathesis)

Ring-opening metathesis is used as a method of polymerization.

Usually, it is applied most often when ring opening creates a

relief of strain, as in some bicyclic alkenes.

n
Ru
[Ru] [Ru]
H
Norbornene Norbornene Polymerization Polynorbornene
73
 Olefin Metathesis

In crossed-olefin metathesis, one alkene is converted to a mixture

of two new alkenes.
catalyst
2 CH3CH=CH2 CH2=CH2 + CH3CH=CHCH3

The reaction is reversible, and regardless of whether we start with

propene or a 1:1 mixture of ethylene and 2-butene, the same
mixture is obtained.
The reaction is generally catalyzed a transition metal complex.
Typically Ru, W, or Mo are used. Shown below is Grubb’s catalyst.
p-cy
Cl
Ru CH
Cl 74
p-cy
 Mechanism of Ring Closing Metathesis (RCM) and
Ring Opening Metathesis ROMP

R' N R' N

R' N Vacancy
Dissociation Olefin R"
O O O
Ru CHPh Association Ru CHPh - Olefin Ru CHPh
Cl Cl Cl
p-cy p-cy p-cy

Me
Me
R' N R' N
R' N
R' N − Cl
Ru O O
O Cl Olefin
O Ru CHPh
Ru CHPh Ru CHPh
Cl - Olefin
Ru CHPh Cl Me Cl
Cl Me
Cl Me R"
Me Cl
Me Ru Cl + Vacancy
Me Ru Cl Ru
Cl Cl

75
 Mechanism of Pd(0)−Pd(II)
Heck Coupling Reaction
HBr / Base Br
L
Pd(0)
Base
L
Oxidative Addition
L Reductive Elimination

H Pd Br L
R (II)
L Pd Br
L
R

R
π–Complex R
L
H Pd Br L
(II)
L Pd Br
(II)
β–H elimination L L
R (II)
π–Complex
Pd Br Insertion
H
L
H 76
Pd–σ intermediate
 Mechanism of Pd(II)−Pd(IV) Heck Coupling Reaction

Tetrahedron
63 (2007) 6949

v e E l i m i n at io n −
Reduct i cO
a l of H Br by A
Remov

Attack of AcO−
(shown on the term inal carbon atom
but could be on the internal carbon.
−

−
Chem. Eur. J. −
7 (2001) 1703
77
 Acknowledgements
 Prof. A. K. Singh

 Dr. N. G. Ramesh and other Faculty members

 Management of Instrument Lab, NMR Lab and Single Crystal

XRD Lab (Dr. Monika Aggarwal & Vivek Bagchi)

 Lab mates (Neetu, Pradhumn, Dipanwita & Gyan) and all

other friends

 IIT, Delhi

 CSIR
78

 Prof. R. J. Butcher and Prof. J. E. Drake

 Mechanism of Suzuli Coupling Reaction

Ph—Ar’ Ph—Br
Pd(0)

Ph—Pd(II)—Br
Ph—Pd(II)—Ar’

NaOH
B(OH)4−

OH Ph—Pd(II)—OH NaBr
Ar' B − OH
OH

Ar’—B(OH)2 NaOH 79
Mechanism of Suzuli Coupling Reaction

80
 81

Mechanism of Heck Coupling Reaction

Attack of AcO─ has been shown on the terminal carbon atom but
it could be on the internal Carbon.

Tetrahedron 63(2007)6949
82
Chem. Eur. J. 7(2001)1703
Mechanism of Heck Reaction Pd(II)─Pd(IV)
(a) CH2=CH─Y
(b) Reversible Attack of AcO─ : attack is shown on the terminal carbon atom but
it could be on the internal Carbon.
(c) Oxidative Addition of ArBr
(d) Reversible Loss of AcO─
(e) Migration of Ar to Terminal Carbon
(f) Beta-Hydrogen elimination (g) Removal of HBr by AcO─

Tetrahedron 63(2007)6949
83

Mechanism of Heck Reaction Pd(II)─Pd(IV)

 Spin: 1/2
Natural abundance: 0.89%
Chemical shift range: 5800 ppm(-1400 to 3400)
123
Te NMR Frequency ratio: 26.169742%
Reference compound: Me2Te in C6D6
Receptivity rel. to 1H at natural abundance: 1.64 × 10─4
Receptivity rel. to 13C at natural abundance: 0.961

Spin: 1/2
Natural abundance: 7.07%
Chemical shift range: 5800 ppm(–1400 to 3400)
Frequency ratio: 31.549769%
125
Te NMR Reference compound: Me2Te (90%)
Receptivity rel. to 1H at natural abundance: 2.28 × 10−3
Receptivity rel. to 13C at natural abundance: 13.4

Spin: 1/2
Natural abundance: 7.63%
77
Se NMR Chemical shift range: 3000 ppm (–1000 to 2000)
Frequency ratio: 19.071513%
Reference compound: Me2Se
Receptivity rel. to 1H at natural abundance: 5.37 × 10−4
84
Receptivity rel. to 13C at natural abundance: 3.15
 Nickel Palladium Platinum

Atomic
28 46 78
Number

Electronic
[Ar] 3d8, 4s2 [Kr]4d10 [Xe]
Configuration 4f14 5d96s1
2,8,16,2 2,8,18,18, 0 2, 8, 18, 32, 17, 1
Electrons
per Shell

Common Oxidation States of palladium are 0, +1, +2 and +4. Although

originally +3 was thought of as one of the fundamental oxidation states of
palladium, there is no evidence for palladium occurring in the +3 oxidation
state; this has been investigated via X-Ray diffraction for a number of
compounds, indicating a dimer of Palladium(II) and palladium (IV) instead.
85
Recently, compounds with an oxidation state of +6 were synthesised.
 Octahedral, Tetrahedral & Square Planar

CF Splitting pattern for

various molecular geometry
dx2-y2 dz2
dx2-y2
Octahedral
Tetrahedral dxy dyz dxz dxy
Square planar
M
M M

dz2
dxz dyz
dx2-y2 dz2
dxy dyz dxz
Mostly
Mostlydd8
8
Pairing
Pairingenergy Vs.
energyVs. Small  High
Small HighSpin
Spin (Majority
(MajorityLow Lowspin) spin)
Weak field<<Pe
Weakfield Pe Strong
Strongfield
fieldligands
ligands 86
Strong field>>Pe
Strongfield Pe i.e.,
i.e.,Pd
Pd2+, ,Pt
2+
Pt2+, ,IrIr,+,Au
2+ + 3+
Au3+
 Selenium Tellurium

Atomic
34 52
Number

Electronic [Ar] 4s2 [Kr] 5s2

Configuration 3d10 4p4 4d10 5p4
Electrons 2, 8, 18, 6 2, 8, 18, 18, 6
per Shell

87
 Some more functionalized ditellurides

OH
NMe2 Me2N
NMe2
Te Me Te OH Te Te
Te
NMe2 Te
Fe Fe

Me

Phosphorus Sulfur Silicon Organometallics J. Organomet. Chem.

126 (1997) 291 15 (1996) 1707 437 (1992) 299

88