48537793

Synthesis and Structural Characterization of Divalent
Metal Complexes Supported by Guanidinato Ligands
YEUNG, Lai Fong
A Thesis Submitted in Partial Fulfilment
of the Requirements for the Degree of
Master of Philosophy
in
Chemistry
The Chinese University of Hong Kong
March 2010
Thesis/Assessment Committee
Professor XIE, Zuowei (Chair)
Professor LEE, Hung Kay (Thesis Supervisor)
Professor LEUNG, Wing Por Kevin (Committee Member)
Professor CHAN, Wai Kin (External Examiner)

Abstract
The present research work focused on the coordination chemistry of
guanidinate ligands of the general formula [(C6H3Me2-2，6)NC(N(RR，)N(F^]-. The
first part of this work centers on the synthesis and structural characterization of
bis(guanidinate) metal complexes. The second part deals with the synthesis,
structural characterization and reactivity of mono(guanidinate) metal complexes.
Chapter One gives a brief review on guanidinate metal complexes.
Chapter Two describes the synthesis and structural characterization of the
newly developed unsymmetrical guanidinate ligands
[(C6H3Me2-2，6)NC(NRR，)NR，]-[ R = CeHu, R，= H (L1); R = C 3 H 7 , R ' = H (L2); R
= C e H u , R' = SiMe3 (L3)]. Bis(guanidinate) complexes of the first-row divalent
transition metals (Mn, Fe, Co and Ni) and Group 12 metals (Zn and Cd) were
successfully prepared by metathesis reactions between MCI2 (M = Mn, Fe, Co,
Ni, Zn, Cd) and the appropriate lithium salts [Li(L")(TMEDA)] (n = 1-3).
Monomeric [M(L 1 ) 2 (THF)] (7)，[M(L1)2] [M = Co 12，Ni 15，Zn 17]，[M(L 2 ) 2 ] [M =
Fe 10, Co 13，Ni 16，Zn 18] and [M(L 3 ) 2 ] [M = Mn 9，Fe 11，Co 14，Zn 19] were
synthesized. Binuclear [{M(L 2 ) 2 } 2 (TMEDA)] [M = Mn 8，Cd 20] were also
isolated. Effects of the steric bulkiness of the guanidinate ligands on the
structure of the corresponding metal complexes were examined.
Chapter Three reports on the preparation and structural characterization of
mono(guanidinate) metal complexes supported by the [(CeH3Me2-2，6)NC(N(Cy)
(SiMe3))NCy]_ (L3) ligand. Mono(guanidinate) complexes of Mn(ll) and Fe(ll)
were synthesized by reacting MCI2 [M = Mn, Fe] with one molar equivalent of
i
the lithium guanidinate [Li(L 3 )(TMEDA)] (5). Monomeric [M(L 3 )(TMEDA)CI] [M =
Mn 21，Fe 22] were synthesized. Reaction of [Mn(L 3 )(TMEDA)(CI)] (21) with
LiMe led to the corresponding Mn(ll) guanidinate-methyl complex [Mn(L 3 )
(TMEDA)(Me)] (23). Copper(l) mono(guanidinate) complex [Cu 2 (L 2 ) 2 ] (24) was
also prepared and structurally characterized.
ii
摘要
這個研究工作集中在胍基配體（通用公式：[(C 6 H 3 Me 2 -2，6)NC(N(RR’)N(R)]_)的
配位化學研究，並且分為兩部分。第一部分會集中在雙（胍基）金屬配合物的合
成和結構，而第二部分則關於單（胍基）金屬配合物的合成、結構和活性。
第一章胍基金屬配合物的文獻綜述。
第二章記述新發展的非對稱性的胍基配體[(C6HH3Me2-2，6)NC(NRR’)NR]- [R =
C 6 H h , R ' = H (L 1 ); R = C3H7 R' = H (L 2 ); R = C 6 H N , R，= SiMe 3 ( L 3 ) ] 的合成和結
構。透過復分解方法，利用二價金屬氯化物（金屬：錳、鐵、鈷、鎳、鋅和鎘）
和相應的鋰鹽 [ L i H T M E D A ) ] (n = 1 - 3 ) 反應，成功合成二價的過度金屬（錳、
鐵、鈷和鎳）和第十二組金屬（鋅和鎘）的雙（胍基）金屬配合物。用復分解方
法合成了十二個單節顯性的雙（胍基）金屬配合物：[M(L 1 ) 2 (THO] (7)，[M(L1)2]
[M = Co 12，Ni 15，Zn 17]，[M(L2)2] [M = Fe 10，Co 13，Ni 16, Zn 18]和[M(L 3 ) 2 ]
[M = Mn 9，Fe 11，Co 14，Zn 19]，和兩個兩核的雙（胍基）金屬配合物：
[{M(L 2 ) 2 } 2 (TMEDA)] [M = Mn 8，Cd 20]。另外，亦會描述胍基配體上的烷基取代
基的位阻因素對於相應的雙（胍基）金屬配合物的結構所帶來的影響。
第三章講述採用胍基配體[(C 6 H 3 Me 2 -2，6)NC(N(Cy)(SiMe 3 ))NCy]- (L 3 )所合成的
單（胍基）金屬配合物的合成和結構。透過復分解方法，利用二價金屬氯化物
(金屬：錳、鐵）和相同的摩爾分子量的鋰鹽[Li(L 3 )(TMEDA)] (5)進行反應，產
生了二個單節顯性的單（胍基）金屬配合物：[M(L 3 )(TMEDA)CI] [M = Mn 21，Fe
22]。單（胍基）錳配合物[Mn(L 3 )(TMEDA)(CI)] (21)與甲烷基鋰鹽進行甲基化作
用，合成單胍基-甲基錳配合物[Mn(L 3 )(TMEDA)(Me)] (23)。另外，一價的單（胍
基）銅配合物[Cu 2 (L 2 ) 2 ] ( 2 4 ) 亦被合成 °
iii
Acknowledgement
I would like to express my sincere thanks to my supervisor,
Prof. LEE, Hung Kay, for his advice, guidance in these two years
and the preparation of this thesis.
I am indebted to Prof. MAK, Chung Wai Thomas and Miss
Chan, Hoi Shan Bella for the X-ray diffraction study, and Dr.
CHEUNG, Yu Sun for the assistance of magnetic moment
measureme 门 t.
My deepest gratitude goes to my labmates, Miss YAO,
Shuang, Miss KU, Ka Wai Wendy and Mr. WONG, Fai George, for
their wholehearted support in these two years. I would like to give
my sincere gratitude to my dearest friends, Miss LAM, Hoi Yi, Miss
LAU, Ting Fong Janet, Miss CHAN, Yi Ling Tobey, Miss LEUNG, Siu
Ki Jay for their continuous encouragement.
Finally, my immense gratitude should go to my beloved
family for their countless love and support.
YEUNG, Lai Fong
September, 2009
iv
Contents
Page
Abstract i
摘要 iii
Acknowledgement iv
Contents v
Abbreviations ix
List of Compounds xi
Chapter One 一 Introduction

1.1 General Background of Amido Ligands 1
1.2 General Background of Guanidinates 2
1.3 Coordination modes of Guanidinate Ligands 5
1.4 A Brief Review on the Coordination Chemistry of Guanidinate

Complexes 7
1.4.1 Main Group Metal Guanidinate Complexes 7
1.4.2 Transition Metal Guanidinate Complexes 12
1.4.3 Rare Earth Metal Guanidinate Complexes 13
1.5 Preparations of Metal Guanidinate Complexes 15
1.6 Applications of Guanidinate Complexes 16
1.7 Objectives of This Work 18
1.8 References for Chapter One 19
Chapter Two 一 Synthesis and Structural Characterization of

Bis(guanidinate) Complexes
2.1 Introduction to Guanidinate Complexes 25
2.1.1 Guanidinate Complexes of the Alkali Metals 25

2.1.2 Bis(guanidinate) Complexes of Divalent First-Row Late
Transition Metals 27
2.1.3 Bis(guanidinate) Complexes of Group 12 Metals 28
v
2.2 Objectives of Our Study 29
2.3 Results and Discussion 30
2.3.1 Synthesis and Structures of Lithium Guanidinates 30
2.3.1.1.1 Synthesis of (L1 = [(C 6 H 3 Me 2 -2 J 6)NC{N(H)Cy}NCy]

(1); L2=[(C6H3Me2-2，6)NC{N(H)Pr'}NPr5 (2) and L 3
=[(C 6 H 3 Me 2 -2，6)NC{N(SiMe 3 )Cy}NCy] (5)) 30
2.3.1.1.2 Physical Characterization of Compounds 1，2 and 5 31
2.3.1.1.3 Molecular Structures of Compounds 1，2 and 5 32
2.3.1.2.1 Synthesis of Solvated Lithium Guanidinate

[Li(U)(THF)] 2 (6) 37
2.3.1.2.2 Physical Characterization of Compound 6 37
2.3.1.2.3 Molecular Structure of Compound 6 38
2.3.2 Synthesis and Structures of Manganese(ll) Bis(guanidinate)

Complexes 40
2.3.2.1 Synthesis of Manganese(丨丨）Bis(guanidinate)

Complexes Supported by L n (n = 1-3) 40
2.3.2.2 Physical Characterization of Compounds 7 - 9 41
2.3.2.3 Molecular Structures of Compounds 7 - 9 42
2.3.3 Synthesis and Structures of Iron(ll) Bis(guanidinate)

Complexes 51
2.3.3.1 Synthesis of Iron(ll) Bis(guanidinate) Complexes

Supported by L" (n = 2，3) 51
2.3.3.2 Physical Characterization of Compounds 10 and 11 52
2.3.3.3 Molecular Structures of Compounds 10 and 11 52

2.3.4 Synthesis and Structures of Cobalt(ll) Bis(guanidinate)
Complexes 57
2.3.4.1 Synthesis of Bis(guanidinate) Cobalt(ll) Complexes

Supported by L n (n = 1-3) 57
2.3.4.2 Physical Characterization of Compounds 12-14 57
2.3.4.3 Molecular Structures of Compounds 12-14 58
2.3.5 Synthesis and Structures of Nickel(ll) Bis(guanidinate)

Complexes 65
2.3.5.1 Synthesis of Nickel(ll) Bis(guanidinate) Complexes

Supported by L n (n = 1, 2) 65
vi
2.3.6 Synthesis and Structures of Bis(guanidinate) Complexes of

Group 12 Metal (M = Zn, Cd) 71
2.3.6.1 Synthesis of Zn(ll) and Cd(ll) Bis(guanidinate)

Complexes Supported by L n (n = 1 - 3 ) 71
2.3.6.2 Physical Characterization of Compounds 17-20 72
2.3.6.3 Molecular Structures of Compounds 17-20 72
2.4 Summary for Chapter Two 82
2.5 Experimental for Chapter Two 83
2.6 References for Chapter Two 92
Chapter Three - Synthesis and Structural Characterization of

Mono(guanidinate) Complexes of Mn(ll), Fe(ll)
and Cu(l)
3.1 Introduction 95
3.1.1 Introduction of Mono(guanidinate) Complexes of the First-

Row Divalent Late Transition Metals 95
3.1.2 Alkyl Complexes of the Late Transition Metals 99
3.1.3 Introduction of Mono(guanidinate) Complexes of Cu(l) 101
3.2 Objectives of Our Study 102
3.3 Results and Discussion 103

3.3.1 Synthesis and Structures of Mono(guanidinate) Complexes
Supported by L 3 103
3.3.1.1 Synthesis of Mono(guanidinate) Metal (M = Mn 21，

Fe 22) Complexes Supported by L 3 103

3.3.2 Synthesis and Structures of Monoalkyl Metal (M = Mn, Fe)
Complexes Supported by the Guanidinate Ligand L 3 110
3.3.2.1 Synthesis of Monoalkyl Metal (M = Mn, Fe)

Complexes Supported by the Guanidinate Ligand L 3 110
3.3.2.2 Physical Characterization of Compound 23 111
vii
3.3.2.3 Molecular Structure of Compound 23 111
3.3.3 Synthesis and Structure of a Copper(l) Guanidinate

Complex Supported by L 2 115
3.3.3.1 Synthesis of a Copper(l) Guanidinate Complex

Supported by L 2 115
3.3.3.2 Physical Characterization of Compound 24 115
3.3.3.3 Molecular Structure of Compound 24 116
3.4 Summary for Chapter Three 119
3.5 Experimental for Chapter Three 119
3.6 References for Chapter Three 122
Appendix 1 - Physical Measurements, X-Ray Structural Analysis 125
Appendix 2 一 NMR Spectra of Compounds 127
Appendix 3 一 Selected Crystallographic Data 139
viii
Abbreviations
Bu n n-Butyl
Buf ferf-Butyl
Cp Cyclopentadienyl
Cy Cyclohexyl
Et Ethyl
Me Methyl
Ph Phenyl
Pr' Isopropyl
R Alkyl
Compounds
DCC A/,A/-dicyclohexylcarbodiimide
DIC A/,A/-diisopropyllcarbodiimide
PMDTA A/，A/，A/，,/V，,A/”-pentamethyldienetriamine
py Pyridine
THF Tetrahyd rofu ra n
TMEDA N，N，AT，/\T-tetramethylethylenediamine
General
, :,...-. • . . .,, :. ...:
calc. Calculated
d Day
dec Decomposition
h Hour
M.p. Melting Point
r.t. Room Temperature
ix
丨丨I
1
‘丨• 丨丨丨
. . . . . . . .
NMR Spectroscopy
•丨 I I
br Broad Signal
d Doublet
m Multiplet
NMR Nuclear Magnetic Resonance
ppm Parts per million
s Singlet
sept Septet
t Triplet
5 Chemical Shift
J Coupling Constant
X
List of Compounds
——~: ^―'—：丨1
丨 ——
Compound Formula Structure Page
CyYH
1 [Li(L 1 )(TMEDA)] 30
\ cLi\N〜/
/N
v_/
r e x p.
2 [Li(L 2 )(TMEDA)] T" N C/ “ N 30
Li
>、、.\c
Cy. ,SiMe3
OCJL cy
5 [Li(L 3 )(TMEDA)] - l" N 0 N " C y 30
Li
>C NC
R I
6 [{Li(U)(THF)} 2 ] h c \l /、Cy h 37
b
H-N
—H V
7 [Mn(L 1 ) 2 (THF)] Î^Mn-oJ 39
H-N \ .
H-N 、^\ rA N-H
, 、 / h
8 [{Mn(L 2 ) 2 } 2 (TMEDA)] d i ^ f 、八〜 N 、丫C 39
H—N \ . 、 I N-H
Me3& N 、N Cy
9 _(L3)2] / N ~{() M n 'C)}- N / 39
°y N N 、SiMe3
^ 、
xi
——
H N 、N Pr7
10 [Fe(L2)2] H X H 51
P" N > N H
Me3Sl N 、N cy
11 [Fe(L3)2] M X ) M 51
Cy N N SiMe3
冷、
A ^
H N 、、N Cy
12 [CO(U)2] - / N ~{(〉。、)H 57
a-
Cy N N
cy
H
Pr \ r^
H N 广
13 [CO(L 2 ) 2 ] )>-N 57
- w N N\ H
a- ^
Me3Si N/ 、N Cy
14 [CO(L3) 2 ] M ( > < ) V " N ! 5 7
Cy N N SiMe3
c \ 々
H\ N, 、N Cy
15 [Ni(U)2] 65
Cy N, N u
H
^、 N, 、N PK
16 [Ni(L2)2] ^ C > O y ~ i 65
^ V「’
Pf N^ 、N H
xii
1111 1 1 11 I I . II I 11 1 1 111'" '""1'

• ' . • -• • . •
H、 N 、、N Cy
17 [Zn(Li) 2 ] 71
Cy N 、N H
各、
H 、乂广
18 [Zn(L2)2] 卜 71
- J ： V、H
t r pr'
cy\ ‘1¾
19 [Zn(L3)2]
Me3&
•
Cy
^
N
N
、氺
、N
Cy
SiMe3
71
H-N 、^\ r-\ N-H

20 [{Cd(L 2 ) 2 } 2 (TMEDA)] 二=：>〒、〜"、〒‘ ；J 二;； 71
H—N \ ^ 、 / N—H
PJ ^ I
SiMe3
Cy—N 7
Cy
21 [Mn(L 3 )(TMEDA)CI] A^-JTl 103

<f 厂 \ .Mn—CI
/ \
口、
SiMe3
C y - N ^ /v
22 [Fe(L3)(TMEDA)CI] f i ^ ^ t l 103
<f 厂 'Fe—CI
\ / \
SiMe3
Cy—N /Cy
23 [Mn(L 3 )(TMEDA)Me] f k ^ C ] 110
\ I Mn——Me
\ z \
xiii
• ； ,. •,…..：；：…I. . I I 」，v..l I . . I. . . I I 11 •;•;. I I : .... ‘ II II • . • . ... . • , ..... .. . . . ： III •…•. “• . 1.. • ‘, , .
Compound Formula Structure Pag©

：：
.… • . . 、 . ：： •'….•
H N — Cu ,丨丨 N ^
24 [CU2(L2)2] ) h \ 115
p / N丨••Cu 一 N PlJ
^ 七
xiv
Chapter One: Introduction
1.1 General Background of Amido Ligands
The development of ancillary ligands as alternatives for
cyclopentadienyl ligands has attracted much attention. Amido ligands, which
consist of two substituent groups on the nitrogen have been received
flourished studies. 1 ’ 2 A general structure of amido ligands is illustrated in Chart
1-1. Amido ligands provide two tunable substituent groups on the nitrogen
center. Therefore, they provide a great potential in ligand design. However, the
steric bulkiness of simple amido ligands is sometimes not bulky enough to
stabilize unusual oxidation states of metal ions.
N-functionalized amido ligands have been developed to enhance the
steric flexibility of amido ligands. /V，AT— chelating amido ligands are formed by
attaching the nitrogen atom of simple amido ligands with amino-containing
substituents. Owing to the flexibility in ligand design, chelating amido ligands,
such as pyridyl amido ligands,3 diketimate ligands,4 amidinate ligands,5
guanidinate ligands 6 and triazenide ligands,7 have received much attention and
have been widely used in organometallic chemistry. Some examples of
chelating amido ligands are depicted in Table 1-1.
R R'
\ /
N
㊀
R,R' = H, alkyl, aryl, silyl
Chart 1-1 1
1
Table 1-1. Examples of A/,A/-chelating amido ligands
I W ,A/,che.ating amido Examples
ligands
9
Me
Me,、N
n N
rS N N
-r ㊀ ©
I r Rastson et al. 3a Kempe et a/.3b
㊀
Pyridyl amido ligands r^î Me
II J II J ^-Me
N^^Bu' Me^^N N"
© ㊀
Lee et al. - 3b 3c
RVVR' M w M e B W
I； ©、丄 /N M N\
^N N Ar^ Âr Ar^ 、Ar
Ar = (C6H3Pr'2-2,6)
Diketiminato ligands
Power et a/.4a Holland et a/.4b
P Sanger et al. 5a Cotton et al.5b
JL /R" Pr'" Ph
Amidinato ligands
\ Pr'"
Lee et a 1.5
M e 3 S i \ ^SiMe 3 Ph、 H
N 、 ^ 、N'
Cy、JL /Cy Ph、X ^Ph

N ^ N N ^ N N ^ N
Guanidinato ligands Zhou etal.^ Bailey et a/.9
Triazenido ligands pr/ u pr/

Gibson, Marshall et al. 7
2
1.2 General Background of Guanidinates
Guanidinate monoanions are Y-shaped CNNN containing ligands with a
general formula of [RNC(NR' 2 )NR"]" (R, R，，R" = H, alkyl, aryl or SiMe 3 ) (Chart
1-2).6
R'\
N
R \ 丄 /R"
Chart 1-2
The steric and electronic properties of these versatile and flexible ligands can
be modified by changing the R, R' or R" substituents on the nitrogen atoms.
The coordination properties of guanidinates are very similar to those of
amidinates and triazenates. The major difference between these ligands is the
presence of an additional substituted nitrogen centre. It allows the
delocalization of the lone pair electrons to the additional nitrogen atom and
leading to two resonance structures (Chart 1-3): the 1,3-diazaallyl and iminium/
diamide resonance forms of guanidinate. Therefore, guanidinates have a
strong 兀―donor ability. Guanidinate ligands are expected to increase the
electron density on the metal centre and reduce the oxidation potential of the
metal ions.
© ©
1,3-diazaallyl iminium/diamide
Chart 1-3
The beginning of guanidinate coordination chemistry dates back to the
year of 1968 when Wade et al. reported the first guanidinate complex
[(Me2N)2C=NLi]2.8 The reaction of 1,1,2,2-tetramethylguanidine with MeLi
produced the dimeric [(Me2N)2C=NLi]2. However, the guanidinate ligand in the
3
latter complex is bound through the imine nitrogen which is very similar to the
bonding mode of neutral guanidine. Guanidinates are found to adopt a variety
of coordination modes: monodentate, chelating and doubly/triply bridging
modes. The first report of chelating guanidinate complexes was published by
Bailey et al. in the year of 1996.9 Treatment of the chloro-bridged dimers
[ { R h ( n - C 5 M e 5 ) C I 2 } 2 ] 2 or [{Ru(n-MeC6H4Pr/-jD)CI2}2]2 with a 1,2,3-
triphenylguanidine [(PhN)C(NHPh)2] gave the corresponding guanidinate
complexes [Rh(n-C 5 Me 5 Mn 2 -(NPh) 2 CNHPh}CI] or [Ru(n-MeC 6 H 4 Pr / -p){n 2 -
(NPh)2CNHPh}CI] (Chart 1-4). Since then, studies of guanidinate ligands have
attracted an increasing attention and a number of complexes have been
reported. Guanidinate ligands can stabilize metal ions of unusual oxidation
states. 15,35 In addition, metal complexes supported by guanidinate ligands were
proven to be useful in catalysis23，24，36 and material science. 25
Me
M e - ^ ^ ^ - M e M e — P r 7
Me; I Me I
Ph—N \ Ph—N \
\ Ph \ Ph
H H
Bailey et al.9
Chart 1-4
4
1.3 Coordination Modes of Guanidinate Ligands
Guanidinate ligands were found to adopt different coordination modes
(Chart 1-5). Their coordination modes depend on the metal ions they bind to
and the size of substituents on the nitrogen atoms.
N ^N N
R 、人 R 、丄 ^R" R 、丄 /R"
I I I \ /
M M M M
Monodentate Bridging Bidentate

Chart 1-5
Monodentate mode:
In this coordination mode, only one nitrogen atom of a guanidinate ligand is
sigma-bonded to the metal center. Sterically very bulky substituents on the
nitrogen atoms can give rise to this type of bonding mode. No example of this
coordination has been reported in the literature. However, scant examples
were observed in the amidinate analogues.
Examples:
Pr'-N N-Pr' 、[ t N , J
I. Et x\ Et
、/L'\ z M e <、"V NMe2
Arnold et a/.10a Jones et a/.10b
Bridging mode:
This bonding mode is usually related to dinuclear metal complexes with short
metal-metal distances to form a M2NCN ring. Small substituents lead to a
5
more parallel orientation of the nitrogen lone pairs, favouring a bridging
pattern. This coordination mode is often found in Group 11 metal complexes.
Examples:
H、zPr/ Me^ Je
II f^：：
Pr'" 丫 Pr' Pr'" 丫、Pr'
Pr 1 H Me^ Me
Coyle et a/.11a Barry et a/.11b
Bidentate mode: .
This bonding mode is commonly observed in most guanidinate complexes. In
this bonding mode, a sigma-sigma coordination with two nitrogen atoms of a
guanidinate anion is bonded to the metal center. A highly strained four—

i 1
member ring M(NCN) is resulted. Bulky substituents on the nitrogen atom
induce a convergent orientation of the nitrogen 丨one pairs, favoring the
chelating mode.
Examples:
Me ?iMe 3
/ Pr' / P^
Me — N / Me 3 Si — N / ,___v
W N y N r A
Pr'-N,C.. I .„CI Ph — N ' . - . l 1 "、CI,,,,..LiZ0\/
Pr'—N巧、CI 丨、、、
Me — N N 、. Me 3 Si— ？ \
\ Pr1 \ Pr'
Me SiMe 3
Mullins et a/.12a Trifonov et al.12b
6
1.4 A Brief Review on the Coordination Chemistry of Guanidinate
Complexes
Guanidinates have been widely used as ligands to form complexes with
metals from all blocks of the Periodic Table. Bulky guanidinate ligands are
capable of stabilizing low oxidation-state and highly electron-deficient main
group, early/middle/late transition and rare earth metal complexes.
1.4.1 Main Group Metal Guanidinate Complexes
Group 1 Metal Complexes
Alkali metal guanidinates are useful starting materials. They are frequently
used as ligand—transfer reagents for the preparation of transition/rare earth
metal guanidinate complexes. They are often used without isolation and
purification. Hence, the solid state structures of alkali metal guanidinates are
rarely reported.8’13 Alkali metal guanidinates are readily synthesized by the
reaction of carbodiimides with appropriate metal amides. Alkali metal
guanidinate complexes often exist as dimers or trimers in the absence of
donor ligands or solvents (Chart 1-6). 13b
Cy Cy
Me3Si \ / SiMe3
务 N:
Me3Si c/V .^XCy SiM63
Na Na
V/i
N N^
C / ^ "Cy
N
Me3Si^ 、SiMe3
Cy、 Cy Cy Cy
\M ,• / SiMe-, \ / y
Me 3 Si N—Li、,n / Me 3 Si N/„. SiMe 3
“。乂
M V, ,
么广、
\ SiMe 3 / V^KCjr// \
Me 3 Si N—Li Cy Me 3 Si SiMe 3
/ / \
Cy Cy Cy
Arnold ef a/.13b
Chart 1-6
7
Guanidinate complexes of the alkaline earth metals are rare. Only few
examples have been reported. 14 Beryllium(ll) guanidinates were not known.
The first alkaline earth metal guanidinate complex was reported by Chang and
coworkers.143 The magnesium(ll) guanidinate complex [Mg{r|2-
(Pr'N)2CNPr'2}2(THF)] (Chart 1-7) was prepared by the insertion reaction of
Pr'N=C=NPr / into the Mg-N bond of [{Mg(NPr') 2 } 2 ]. Later, calcium(ll) and
strontium(ll) bis(guanidinate) complexes [M{r|2-(CyN)2CN(SiMe3)2}2] (M = Ca,
Sr) were successfully prepared by Harder and coworkers (Chart 1-8). 14b
O cy\ /cy
Pd ？ P— Me 3 Si\ N \ 、、N SiMe 3
N ^ ^ N Me Si N N SiMe 3
' / \ \ . / \
Pr' Pr7 Pr' Pr' Cy Cy
M = Ca, Sr
Chang et al.Ua Harder and coworkers1413
Chart 1-7 Chart 1-8
Recently, Jones and coworkers have reported a peculiar example of
magnesium(l) guanidinate complex [Mg2{n2-(Pr/N)2CN(C6H3Pr/2-2,6)2)2] (Chart
1-8). 15 The bulky guanidinate ligand is able to stabilize the unusual +1
oxidation state of the magnesium(l) ion with the formation of a Mg-Mg bond.
Ar Ar
Pr\ N、 /Pr'
N-{( Mg—Mg.、))~N
p Z N , N X
Pr/
Ar Ar
Ar = C6H3Pr'2-2，6
Jones et a/.15
Chart 1-8
8
There are many examples of guanidinate complexes of the Group 13 metals.
iib，ie j h e first Group 13 metal guanidinate complex [Cl2AI{n 2 -NPr / C(NPr / 2 )NPr / }]
(Chart 1-9) was reported by Chang et a/.16a It was prepared by the insertion
reaction of Pr / N=C=NPr / into the Al-N bond of [AI(NPr' 2 )CI 2 ].
Pfx
〜 N 、、CI
Pr'
MX N
/
CI
Pr 1
Chang ef a/.16a
Chart 1-9
Sterically bulky guanidinate ligands are useful in stabilizing Group 13 metals in
their +1，+2 or a mixed oxidation state. 16-18 Some examples of these Group 13
guanidinate complexes are shown in Chart 1-10. Group 13 guanidinate
complexes have diverse applications. They have been employed as catalysts
and precursors for chemical vapor deposition. 130 Interestingly，gallium(l) and
indium(l) guanidinate complexes have been used as sigma—donor ligands in
other metal systems, such as platinum and nickel, forming heteroatom metal-
metal bonds (Chart 1-11). 18

Ar
\ 〜
Ar P— N、 CI Ar Ar
\ \ // \ , / / \
Cv N、 .In N Pr' Cy、 N、
)K M X
、丨
> P^ ) ' <

Cy N Ar c / 、N Pr' Cy N SiMe3
a/ Ar Ar
ln(l) ln(ll) Ge(lll)
Jones et a/.16b
Chart 1-10
9
Ar Cy
\ ‘ Ar Cy
F \ ,N
Ar / 1 / N -Cy
cy a/ E r,rAr vT、Ga-z
HN-cv 着 K e y
A/ i ^ ^ S I \
Cy r Ar Cy
Pt(0) Pt(ll)
Jones eta/. 18
Chart 1-11
Very few studies of guanidinate complexes of divalent Group 14 metals have
been reported. 19 Junk and coworkers have reported the first example of a
stable lead(ll) guanidinate complex [([J-CI)2Pb2{n2-N(Ar)C(NCy2)N(Ar)}2] (Ar =
C6H3Pr/2-2,6) (Chart 1-12). 19a It was prepared by metathesis reaction of [Li{r|2-
N(Ar)C(NCy 2 )N(Ar)}] and PbCI 2 to afford a binuclear lead(ll) complex.
Ar Ar
\ /
Cy. N CI、、、N Cy
\ X、))^/
A/ 、Ar
A r = C6H3Pr^-2.6
Junk and co-workers19a
Chart 1-12
Considerable efforts have been devoted in the development of homonuclear
alkyne analogues of the heavy main group 14 metals. A number of REER (E =
Si(l), Ge(l), Sn(l), Pb(l); R = bulky aryl or silyl group) compounds have been
prepared and the nature of the E - E bond in REER has been studied in many
theoretical studies.20 Since guanidinate ligands are useful in stabilizing
monovalent Group 13 compounds, they were also utilized to stabilize dimeric
germanium(l) compounds, analogous to digermynes [RGeGeR]. 21 Chart 1-13
shows the structure of [LGeGeL’] (L = [(Pr^NJCCNCeHaPr^.e)^-). 21
10
Ar
\
Pri M
\ / / \ Ar
N-(( Ge
,/ \ / N Pr'
Pr' N \ X N\ /
A / .Ge JV-N
Ar •、乂/ \
N pr'
\
Ar
Ar = C6H3Pr/2-2.6
Jones et a/.21
Chart 1-13
Studies of Group 15 metal guanidinates have received little attention. 22 Only
two examples of Group 15 guanidinates have been reported until now. The first
Sb(lll) guanidinate complex was reported by Bailey et al. in 1997 (Chart 1-14).
22a It was prepared by the reaction of 1,2,3-triisopropylguanidine
[Pr'NCCNHP^] with antimony triamide [Sb(NMe 2 ) 3 ]. The Sb(lll) complex
contains both monoanionic and dianionic guanidinate ligands, so that the +3
charge of the antimony is balanced. It is a rare example of a mixed-ligand
complex. Guanidinate ligands have also been used to stabilize a diarsene
compound (Chart 1-15). 22b
Cy、_/Cy
H
'
Pr'— N ^ N
/
Pr'
Ar、 1
^
、N々nz
A
A「 ,
Y\ I +
pp—N,,, \ As As
Zs/b 丨 1
\ I A「z I Ar
Pr'- N Pf c , "Cy
Bailey et al.22a Jones et al.22b
Chart 1-14 Chart 1-15
11
1.4.2 Transition Metal Guanidinate Complexes
Earlv Transition Metal Complexes
Guanidinate complexes of the early transition metals have received a great
attention due to their diverse applications. They were demonstrated to exhibit
catalytic activities, such as polymerization, 2 3 hydroamination, 2 4 and
applications in material science. 25 The first transition metal guanidinate
complexes, reported by Lappert et al. in 1970，were the titanium(IV) and
zirconium(IV) derivatives, [(Me 2 N) 2 M{r] 2 -NCyC(NMe 2 )NCy} 2 ] (M = Ti，Zr). 26
They were synthesized by the reaction of CyN=C=NCy with M(NMe2)4. This
methodology has inspired the later development of guanidinate complexes.
Middle Transition Metal Complexes
Studies on middle transition metal guanidinate complexes have been focused
mainly on structural studies. Middle transition metals, such as Cr(ll), Mo(ll) and
V(ll), have the preference of multiple bond formation between two metal
centers. Chromium(ll) ion has the ability to form a high-multiplicity, quadruple
metal-metal bond.27，30 Vanadium(ll) can form triply bonded V24+,28,30 whereas
molybdenum(ll) can form quadruply bonded Mo24+.29，30 A M24+ guanidinate
compound, [Mo 2 {|>n 2 -(NPh) 2 CN(H)Ph} 4 ] (Chart 1-17)，was first reported by
Bailey et al. 29a Later on, Cotton and coworkers have reported the synthesis of
\/24+，Cr24+ and Mo24+ compounds supported by the hpp_ ligand (Chart 1-16). 30
The M24+ core in these compounds are all tetrabridged by four guanidinate
ligands to form a "paddelwheel" structure. The metal-metal bond containing
compounds are not only interesting in terms of structural studies, but also their
applications. They have found applications in catalysis, medicine, and
12
supramolecular chemistry.2913，31 In this regard, middle transition metal
guanidinate complexes have attracted much attention.
hpp-
Chart 1-16
Late Transition Metal Complexes
Second-row late transition metal guanidinate complexes have been
extensively studied9-32 as compared to their first-row counterparts. 33 This may
be ascribed to the unstable nature of the first-row late transition metal
complexes. Late transition metal complexes featuring covalently bound n—
donor amide ligands are important intermediates in a number of biological
systems and catalytic processes. 38 They are relatively unstable and reactive as
compared to the early transition metal counterparts. As a result, late transition
metal guanidinate complexes are less common. Accordingly, much research
interest has been attracted to the synthesis and reactivity studies of these
reactive species.
1.4.3 Rare Earth Metal Guanidinate Complexes
Lanthanide(lll) guanidinate complexes were shown to exhibit a high catalytic
activity toward the ring-opening polymerization of lactones，lactides and
trimethylene carbonate (TMC). The first example of lanthanide(lll) guanidinate
complexes were reported by Zhou et al. in 1998.34 The lanthanide(lll)
guanidinate complexes of [M{r| 2 -CyNC[N(SiMe) 2 ]NCy} 2 (|j-CI) 2 Li(L) 2 ] (M = Sm,
丫b; L = Et2〇，1/2TMEDA) were synthesized by metathesis reaction of the
13
lithium guanidinate [Li{r| 2 -CyNC[N(SiMe)2]NCy}] and the corresponding LnCb
(M = Sm，Yb). The lanthanide(lll) ate-complexes were subsequently reacted
with [UE(SiMe3)2] (E = CH, N) to yield the corresponding lanthanide(lll) alky I
and amido complexes [{CyNC(N(SiMe 3 )2)NCy} 2 M{E(SiMe 3 )2}] (M = Sm, Yb; E
= C H , N) (Chart 1-17).
SiMe3 SiMe 3
/ Cy / Cy
Me 3 Si — N / Me 3 Si—N /
Me 3 Si—N \ Me 3 Si—N \
\ Cy \ Cy
SiMe3 SiMe 3
Ln = Sm, Yb
L = Et 2 0, 1/2TMEDA
E = CH, N
Zhou et a/.34
Chart 1-17
Lanthanide(ll) ions have a strong reducing power. Guanidinate ligands can be
utilized to reduce the oxidation potential of lanthanide(ll) ions. However,
lanthanide(ll) guanidinate complexes are still rarely investigated. The only one
example of neutral homoleptic lanthanide(ll) guanidinates，[Ln{r| 2 -
N(C6H3Pr/2-2J6)C(NCy2)N(C6H3Pr/2-2l6)}2] (Ln = Sm, Eu, Yb), was reported by
Jones et al. in 2007. 35 The mononuclear lanthanide(ll) guanidinate complexes
have been prepared by reacting lanthanide(ll) iodide with the potassium salt of
the corresponding guanidinate ligand [K{n2-N(C6H3Pr/2-2,6)C(NCy2)N(C6H3Pr/2-
2,6)}]. Guanidinate complexes of the actinide remain unknown.
Ar Ar
\ /
Cy N 、， N Cy
M/ n : :、H:
Cy N N Cy
/ \
Ar Ar
Ln = Sm, Eu, Yb
Ar = C6H3Pri2-2.6
Jones et a/.35
Chart 1-18
14
1.5 Preparations of Metal Guanidinate Complexes
Several synthetic methods are commonly employed for the preparation
of metal guanidinate complexes. They include the following:
1. Metathesis reactions of alkali metal guanidinates with metal halides:
yM,[(R,N)2CNR2] + MCIX • M[(R'N)2CNR2]yClx.y + M'Cly
Example:
Pr'
I Pr1
PH一N /
-2LiCI
2 equiv LKPr'NqNKhOPriNPr^} + FeCI3 ^ PH —N,,,.^—C|
PH — N ^ I
Pr7 — N \
\ P"
. Pf
Richeson et a/.33
2. Reactions of guanidines with metal alkyls:
y[(R,NH)2CNR'] + MRX • M[(R'N)2CNHR,]y(R)x.y + y(HR)
Example:
Cy Cy
Me3Si\ ^SiMe 3 /
N Me3Si N 、、N SiMe3
ZnMe2 + cy、人 zy ^ :N~<(>、hN:

u Me3Si N N SiMe3
/ \
Cy Cy
Coles and Hitchcock37
3. Insertion reactions of metal amides and carbodiimides:
M(NR2)x + x [R'NCNR'] ^ M[(R_N)2CNR2]X
Example:
cy\ /y
Me 3 Si\ N ^ 、、N SiMe3
Zn[N(SiMe3)2]2 + CyN=C=NCy • : N Z n '
MeaSi7 N^ 、N SiMe3
Cy 7 X Cy
Coles and Hitchcock37
15
1.6 Applications of Guanidinate Complexes
Guanidinate—supported transition metal complexes play an important
role in catalytic reaction and material science. They are reported to be effective
catalysts in polymerization reactions 23 ' 36 and hydroamination. 24 In addition,
guanidinate complexes are found to have broad applications in material
science. 25 They contain the properties well-suited for the use of volatile
precursors for the atom layer deposition (ALD) and chemical vapor deposition
(CVD). Several patents of using metal guanidinate complexes in ALD or CVD
are reported 39 . Some examples of guanidinate complexes and their
applications are shown in Table 1-2.
Table 1-2. Applications of some metal guanidinate complexes

Metal Guanidinates Applications References
•
！！！ I ！！
严Me3即 Low pressure chemical vapor Carmalt et al. 25a
Me3si—n N/ deposition (CVD)
Pr / —N/,.. ' .^Cl
即-N〔 |、CI
Me 3 Si—N \
\ Pr'
SiMe3
p— Hydroamination of alkynes Richeson et a 1. 24

Me—N /
二 + R
Me—N \ .
\ Pr7
Me
R = H, Ph
严Me3即 Metal-organic chemical vapor Devi et al. 25b- c

Me3si—n / Me deposition (MOCVD)
I I
二X N、r
N — E t
Pr I、N-Me
K n 、Et
Me 3 Si—N \ 匕
个
\ P"
SiMe3
M = Hf, Zr
16
I Ill — i — — ^ Mill ^^^^îmm^^mmmmmm^^mmmm^mm^^^^^^^^^^mmm^^m
Metal Guanidinates Applications References

i — — — — — — — I II III I I I • MMMMMMMMMMMMMM^^M^^MM^^WMM^^MâtMM^MMM-M-M^M^^M^MM^^^n^MB MMMM^MM^^MMMMMMMMMMMMMMMMMMMBMMMM
Ar\ ci ci 'Ar Ethylene polymerization Zhou et a/.23a

Me\ N 、I ^CL |' N Me J r J
Me N、 I I 'N U Me
A/ Cl 、Ar Cl
Ar = C6H3PK2-2.6
/Me siMe3 Ethylene polymerization Zhou et a/.23b

Me~-N I SiMe 3
M M X ，
Me3Si、N、丄/ NVN
Me 3 Si—N Me
Cl \...
“ m
Me—N \\ SiMeJ3
SiMe3
Me J
M = Hf, Zr
产Me3p— The ring-opening Trifonov et a/.36a
Me3si—n n , polymerization of a racemic
p, y I lactide
Pr — N//,.,' v
Pr'—N*^ j
Me33Si—N \ .
\ Pr'
SiMe3
X= OBuf Ln = Y, Nd, Sm, Lu
X= OPr' Ln = Y, Nd, Lu
f Olefin polymerization: Trifonov et a/.36b

Me3si-N / polyethylene
p h - n ^ I ..,、ci,,,,.. . / O polypropylene
fv—j polystyrene
Me 3 Si — N \
\ PH
SiMe 3
7
Ph The ring-opening Shen et a/.36c
ph、N c /Cy polymerization of
\ n N/
cy-N, I、、 7
Ph trimethylene carbonate(TMC)
N\ Ph
Ph—n、 \CyCy Amidation of aldehydes with Qian et a/.36d

Ph amines
Ln = Yb, Sm, Nd
SiMe3 Polymerization of rac-lactides Carpentier,

; c
Me3si-N / y and S,S-lactides Trifonov et a/.36e
Y \ h4 ^ )
cy—Nr I 、 B < 、、
Me3Si—N \
\ P"
SiMe 3
Ln = Yb, Sm, Nd
17
1.7 Objectives of This Work
The chemistry of metal guanidinate complexes has attracted increasing
attention in recent years. A number of guanidinate ligands have been
developed as alternatives of cyclopentadienyl ligands. Bulky guanidinate
ligands are capable of stabilizing main-group metal, transition metal and rare
earth metal complexes. They exhibited a rich structural and reaction chemistry.
The steric and electronic properties of guanidinate ligands can be
modified by introduction of various substituents to the nitrogen atoms. Both the
steric and electronic nature of guanidinate ligands play an important role in
determining the coordination chemistry, stability and reactivity of the
corresponding metal complexes.
In the present research work, we aimed to prepare transition metal
complexes supported by a series of bulky guanidinate ligands (Chart 1-19).
The effects of A/-substituents on the coordination chemistry of the
corresponding complexes were examined.
f 人力各 N ，各 N - C y
L 1 L2 L3
Cy = cyclohexyl
Chart 1-19
18
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34.Zhou, Y.; Yap, G. P. A.; Richeson, D. S. Organometallics 1998，17, 4387-
4391.
35.Heitmann, D.; Jones, C.; Junk, P. C.; Lippert, K. A.; Stasch, A. Dalton Trans.
2007，187-189.
36. (a) Ajellal, N’； Lyubov, D. M.; Sinenkov, M. A.; Fukin, G. K.; Cherkasov, A.
V.; Thomas, C. M.; Carpentier, J.; Trifonov, A. A. Chem. Eur. J. 2008，14,
5440-5448. (b) Trifonov, A. A.; Fedorova，E. A.; Fukin, G. K.; Bochkarev, M.
N. Eur. J. Inorg. Chem. 2004，4396-4401. (c) Zhou, L.; Yao, Y.; Zhang, Y.;
Xue, M.; Chen, J.; Shen，Q. Eur. J. Inorg. Chem. 2004，2167-2172. (d)
Qian, C.; Zhang, X.; Li, J.; Xu, F.; Zhang, Y.; Shen, Q. Organometallics DOI:
10.1021/om900120v (e) Skvortsov, G. G.; Yakovenko, M. V.; Castro, P. M.;
Fukin, G. K.; Cherkasov, A. V.; Carpentier, J.; Trifonov, A. A. Eur. J. Inorg.
Chem. 2007，3260-3267.
37. Coles, M.; Hitchcock, P. B. Eur. J. Inorg. Chem. 2004, 2662—2672.
38.(a) Bryndza, H. E.; Tam, W. Chem. Rev. 1988， 88, 1163-1188. (b)
Roundhi丨I，D. M. Chem. Rev. 1992，92, 1-27.
39.(a) Denk, M.; Fournier, S. US 2005042372，2005. (b) Wallbridge, M. G. H.;
23
Philips, P. R.; Barker, J. GB 2295393, 1996. (c) Thenappan, A.; Lao,丄；
Nair, H. K.; Devi, A.; Bhakta, R.; Milanov, A. WO 2 0 0 7 0 0 5 0 8 8 ， 2 0 0 7 . (d)
Chen, T.; Xu，C.; Baum, T. H•； Hendrix, B. C.; Cameron, T.; Roeder, J. F.;
Stender, M. WO 2 0 0 7 1 4 2 7 0 0 ， 2 0 0 7 .
24
Chapter Two: Synthesis and Structural Characterization of
Bis(guanidinate) Complexes
2.1 Introduction to Guanidinate Complexes
Guanidinates have been widely used in transition-metal and lanthanide
chemistry to form complexes which exhibit a wide variety of coordination
chemistry and reactivity.1，2 They offer a greater potential in ligand design than
that of Cp ligands. In addition, their ability to exhibit three different bonding
modes to metal centers are suitable for studying the steric and electronic
factors that favor or disfavor particular geometric, coordination and reactivity
properties of the resultant metal complexes. Reports on complexes supported
by guanidinate ligands were scarce until the early 1990s. Since the first report
in 1996 on the use of monoanionic 1,2,3-trisubstituted guanidinates
[(NR)2CNHR]_ as chelating ligands,3 a number of complexes of main-group,
transition metal, and rare earth metal have been reported in the literature.1，2
The following includes brief reviews on guanidinate complexes of the alkali
metals, bis(guanidinate) complexes of first-row divalent late transition metals
and Group 12 metals.
2.1.1 Guanidinate Complexes of the Alkali Metals
As mentioned in the previous chapter, alkali-metal guanidinate
complexes are useful starting materials for metathesis reactions. Although they
are widely employed as synthetic precursors, their molecular structures are
still not well documented. 4-7
25
The alkali metal centre is usually coordinated by donor solvents (THF,
Et2〇）or donor ligands (TMEDA, PMDETA)，which are usually added to
facilitate the isolation of alkali-metal guanidinate complexes. Chivers and
coworkers have reported the solvated lithium guanidinate complex [Li(THF){|j-
n2-(NBuf)2C(HNBuO}2Li].7 The lithium guanidinate was synthesized in a low-
temperature reaction between 1,3-di-fe/t-butylcarbodiimide and lithium tert-
butylamine in THF (Scheme 2-1).
Bu、 I Bul
2 Bu^^NBuf + 2 LiNHBu f — ^ • _ h N、、.. ' ' " " N 7 BU1
Bu f N < 、 N H
Bu" W
Scheme 2-1
In the absence of donor solvents or ligands, base-free alkali metal
guanidinate complexes usually exhibit a high degree of association.
Unsolvated alkali-metal guanidinate complexes have been reported by Arnold
et a/.6 These alkali-metal guanidinates [M{CyNC(N(SiMe 3 ) 2 )NCy}] n (M = Li, n =
2; M = Na，r? = 3; M = K, r? = 2) were prepared by the reaction of CyN=C=NCy
with [MN(SiMe3)2] (Scheme 2-2). A general structure of these compounds
consists of two M+ ions doubly bridged by one guanidinato ligand, forming
dimers or trimers. Their molecular structures are depicted in Chart 1-7.
n CyN=C=NCy + n MN(SiMe3)2 toluene/hexane > [M{CyNC(N(SiMe3)2)NCy}]n
M = Li, n:2
M = Na, n = 3
M = K, n = 2
Scheme 2-2
26
2.1.2 Bis(guanidinate) Complexes of Divalent First-Row Late Transition
Metals
Previous work on late transition metal guanidintes were focused mainly
on second-row late transition metals.3-8 Studies on divalent first-row late
transition metal complexes are scarce. 9 It is believed that the reactive M - N
bond of first-row divalent late transition metal complexes renders their
preparation and characterization difficult to carry out. 23 The first homoleptic
iron(ll) bis(guanidinate) complexes [Fe{p-r| 2 -(RN) 2 C(HNR)}{r| 2 -(RN) 2 C(HNR)}] 2
(R = Cy, Pr') were reported by Richeson et a 1. 9 These complexes were
synthesized by treatment of iron(ll) bromide with two molar equivalents of the
corresponding lithium guanidinates [Li{r|2-(RN)2C(HNR)}] (R = Cy, Pr') (Scheme
2-3). The guanidinate ligands exhibit two different coordination modes. After
that, there has been no other report on first-row divalent late transition metal
guanidinate complexes. The scarcity of divalent first-row late transition
guanidinate complexes has attracted an increasing attention on their
coordination chemistry. In fact, first-row late transition metal complexes were
proven to be useful in catalysis and material science.10，11 Therefore, transition
metal guanidinate complexes may have a great potential in practical
applications.
H . 力 R\ /R
N R N,, I \、、N R
2 equiv + FeCI2 ^ 'Fe Fe'。N
\ / \-\ M ^ \ I V l
Li XR
R = Pr', Cy N
H^、
Scheme 2-3
27
2.1.3 Bis(guanidinate) Complexes of Group 12 Metals
As zinc(ll) complexes have been shown to be active towards the ring-
opening polymerization of lactones, guanidinate complexes of Group 12 metals
have also attracted much attention.12-13 The first zinc(ll) guanidinate complexes
[Zn(n2-{(RN)2C(N(SiMe3)2)2}2] (R = Cy, Pr') were reported by Coles et a/.13
These complexes could be prepared by several synthetic routes (Scheme 2-4).
The homoleptic zinc(ll) guanidinates were found to be active in the ring-
opening polymerization of lactides. Recently, zinc(ll) guanidinate complexes
have also been employed in the studies of zinc-metal bonded compounds.
Mono(guanidinate) zinc(ll) complex [Zn{n 2 -(Pr / 2 NC(NAr) 2 )}CI] (Ar =
C6H3Pr'2-2，6) was used to form zinc-gallyl complex
[{Pr/2NC(NAr)2}ZnGa{[N(Ar)C(H)]2}] which contains a heteroatom metal-metal
bond (Chart 2-1). 14 Until now, no example of cadmium and mercury
guanidinate complexes has been reported in the literature.
Me3Si\N/SiMe3
ZnMe2 + R、人.R \
"N N \
H \
\ R R
\ \ /
\ Me3Si^ 、、 N SiMe3
Zn[N(SiMe3)2]2 + RN=C=NR )——-
/ Me3Si N N SiMe3
/ R, 、R
/ R = Cy, PH
Me3Si\N/SiMe3 /
Zn[N(SiMe3)2]2 + R I R 丨
"N N''
H
Scheme 2-4
Ar Ar
\ /
Pr'\ N、、、N)
N 、( Zn-Ga、J
Pr' N 、N^
Ar7 Ar
A r = C 6 H 3 PiV2,6
Jones et a/.18
Chart 2-1
28
2.2 Objectives of Our Study
Guanidinate ligands have attracted an increasing attention in
organometallic chemistry. Variation of substituents on the nitrogen atoms of a
guanidinate ligand provides a great potential in ligand design through
modification of their steric and electronic properties. Guanidinate complexes of
the early transition metals have been extensively studied. However, late
transition metal guanidinates are rare. In this regard, we are interested in the
studies of first-row divalent late transition metal guanidinate complexes.
Homoleptic first-row divalent late transition metals (M = Mn, Fe，Co, Ni)
supported by unsymmetrical guanidinate ligands of the general formula
[(C6H3Me2-2，6)NC(NRR，)NR]- [R，R，= Cy, H (L1); R, R，= Pr', H (L2); R, R，= Cy,
SiMe3 (L3)] were synthesized. The steric effects of the N—substituents of the
guanidinate ligands on the coordination geometry of the corresponding
guanidinate complexes were examined. Bis(guanidinate) complexes of the
Group 12 metals (Zn, Cd) were also prepared and characterized.
29
2.3 Results and Discussion
2.3.1 Synthesis and Structures of Lithium Guanidinates
2.3.1.1.1 Synthesis of [Li(L")(TMEDA)]
(L 1 = [(C6H3Me2-2，6)NC{N(H)Cy}NCy] (1);
L 2 = [(C6H 3 Me2-2 J 6)NC{N(H)Pr / }NPr / ] (2)
and L 3 = [(C6H3Me2-2，6)NC{N(SiMe3)Cy}NCy] (5))
A number of synthetic routes were known for the preparation of
guanidinate complexes.1，2 One of these involves the insertion reaction of metal
amides to dialkylcarbodiimides. This route has often been employed in the
synthesis of lithium guanidinates. As shown in Scheme 2-5, the lithium
guanidinates 1 and 2 have been prepared by the insertion reaction of an
appropriate lithium anilide to RN=C=NR (R = Cy, Pr'). The lithium anilide was
prepared in situ by reacting 2,6-dimethylaniline with LiBun in the presence of
TMEDA. The Li-N bond of the metal anilide was inserted into the N=C=N
moiety of the carbodiimide, affording the lithium guanidinates 1 and 2 in 70%
and 75% yield, respectively.
f ^ C 1. TMEDA, LiBu n , Et 2 0, r.t., 8h N N z R
S^NH ^ \ \ /
1 2. RNCNR, Et 2 0, r.t., 8h Li
1 \、、 \ /
ZN NC
1 R = Cy (70%)
2 R = Pr7 (75%)
Scheme 2-5
The lithium derivative 5 was prepared by reacting the N-silylated lithium
anilide 4 with CyN=C=NCy in diethyl ether as illustrated in Scheme 2-6. The
lithium anilide 4 was prepared according to a modified literature procedure.15，17
30
The lithium anilide 4 was isolated as colorless crystals in 80% yield.
Subsequent reaction of 4 with CyN=C=NCy afforded the lithium guanidinate 5
as colorless crystals in 75% yield. Reaction of compound 4 with CyN=C=NCy
involves the insertion reaction of the amido ligand into the N=C=N moiety,
followed by a 1，3-silyl migration.
f ^ y 1 - LiBu", Et 2 0, r.t., 4h ( ^ Y ^
V^NH “ kAM-SiMe3
nh2 2. Me3SiCI, Et 2 0, r.t., 8h J N
3 (85%)
Cy、N/SiMe3
v- N - s i M e 3
1.LiBu", Et 2 0, r.t.,4h I | cVNCNCy
w I \ /
U Li
, 、
2. Me3SiCI, Et 2 0, r.t., 8h S ^ Et 2 0, r.t.’ 8h
^ ^
4 (80%) 5 (75%)
Scheme 2-6
2.3.1.1.2 Physical Characterization of Compounds 1，2 and 5
Compounds 1，2 and 5 were characterized by 1H and 13 C NMR
spectroscopy, melting-point measurement, elemental analysis and X-ray
crystallography. Table 2-1 shows some physical properties of compounds 1，2
and 5.
Table 2-1 Physical properties of compounds 1, 2 and 5.

Compound Yield (%) Appearance of Crystals M.p. (<>C)
1 70 Colorless 107-109
31
2.3.1.1.3 Molecular Structures of Compounds 1，2 and 5
Crystals of complexes 1，2 and 5 suitable for X-ray diffraction studies were
obtained from diethyl ether (1 and 2) and hexane (5). Figures 2-1，2-2 and 2-3
depict the molecular structures of complexes 1，2 and 5，respectively, with the
atom numbering scheme. Selected bond lengths and angles of the three
compounds are listed in Tables 2-2，2-3 and 2-4.
Compounds 1, 2 and 5 are isostructural with a distorted tetrahedral
geometry around the Li center. Compounds 1 and 5 crystallize in a triclinic
crystal system with the space group P1, whilst compound 2 crystallizes in a
monoclinic crystal system with the space group P2i/n.
Compounds 1，2 and 5 are mononuclear. Each lithium atom is surrounded
by one chelating guanidinate ligand and one chelating TMEDA. The N(1)-C(9)
and N(3)-C(9) bond distances in the three complexes fall within the range of
1.340(3) 一 1.350(4) A and 1.315(3) 一 1.321(3) A, while the N(2)-C(9) bond
distances from the uncoordinated nitrogen are slightly longer, which cover the
range of 1.386(4) 一 1.453(3) A. The difference in the N - C bond lengths can be
attributed to a delocalization of electron density over the N(1)-C(9)-N(3)
moiety. The lone pair electron density of the uncoordinated nitrogen atom N(2)
does not involve in the 71-system.
The L n (n = 1-3) ligands are unsymmetrical. This results in different Li(1)-
N(1)guanidinate and Li(1 )-N(3) gU anidinate distances in the three compounds. The
Li(1)-N(1) g uanidinate and Li(1 )-N(3) gU anidinate distances cover the range of 2.014(5)
- 2 . 0 5 2 ( 4 ) A and 1.974(7) - 1.984(5) A, respectively. The observed bond
length of Li(1)-N(3)(Ar) is longer than that of Li⑴一N(1)(R) (R = Cy, Pr'). It is in
contrast to the reported lithium complex supported by an unsymmetrical
32
benzamidinate ligand [Li{n 2 -PhC(NSiMe 3 )(NC6H 3 Me2-2 ! 6)}(TMEDA)], in which
the bond distance of Li(1)-N(3)(Ar) is shorter than that of Li(1)-N(1)(R) (R =
SiMe3).20 The CN3 moieties of L n (n = 1-3) are planar with the sum of angles
around the central carbon being 360°. Due to the geometric constraint of the
N - C - N moiety, the N(3)-Li(1)-N(1) bite angles of the three compounds are
restricted to 6 8 . 4 ( 1 ) - 68.6(2)°.
There is no significant difference in Li-N gU anidinate bond lengths and N(1)—
Li(1)-N(3) bite angles when changing the substituents (H, Cy, Pr' and SiMe3)
on the nitrogen atoms of guanidinate ligands.
33
C20
C4
Figure 2-1. Molecular structure of [Li(L 1 )(TMEDA)] (1) (30% thermal ellipsoids).
Table 2-2. Selected bond lengths (A) and angles (°) of compound 1.
[Li(L1)(TMEDA)J
L i ( 1 ) 一N ( 3 ) 1.975(4) L i ( 1 ) 一N ( 1 ) 2.052(4)
Li(1)-N(5) 2.150(4) Li(1)-N(4) 2.151(4)
N(1)- C(9) 1.348(3) N(1)-C(1) 1.404(3)
N(2)-C(9) 1.392(3) N(2)-C(10) 1.462(3)
N(3)-C(9) 1.321(3) N(3)-C(16) 1.449(3)
N(3)-Li(1)-N(1) 68.6(1) N(3) - Li(1)-N(5) 128.1(2)
N(1)-Li(1)-N(4) 122.3(2) N(5)- Li(1)一 N(4) 85.2(1)
C(9)-N(1)-C(1) 122.1(1) C(9)-N(1)-Li(1) 85.3(1)
C(1)-N(1)-Li(1) 139.8(1) C(9)一 N(2)—C(10) 124.2(1)
C(9)-N(3)-C(16) 121.2(1) C(9)-N(3)-Li(1) 89.2(1)
C(16)-N(3H~i(1) 149.1(1) N(3)-C(9)-N(1) 116.6(1)
N(3)-C(9)-N(2) 122.1(2) N(1 )-C(9)-N(2) 121.3(1)
34
M a
C20
[Li(L 2 )(TMEDA)]
Li(1)-N(3) 1.974(7) Li(1)一 N(1) 2.030(7)
Li(1)-N(4) 2.096(7) Li(1)-N(5) 2.124(7)
N(1)-C(9) 1.350(4) N(1)-C(1) 1.388(4)
N(2)-C(9) 1.386(4) N(2)-C(10) 1.462(5)
N(3)-C(9) 1.319(4) N(3)-C(13) 1.456(5)
N(3)~Li(1)-N(1) 68.6(2) N(3)- Li(1)-N(4) 123.6(4)
N(1)-Li(1)-N(4) 119.2(3) N(3)-Li(1)-N(5) 129.1(3)
N(1)-Li(1)-N(5) 136.7(4) N(4)-Li(1)-N(5) 85.6(3)
C(9)-N(1)-C(1) 127.0(3) C(9)-N(1)-Li(1) 86.4(3)
C(1)-N(1)-Li(1) 136.8(3) C(9)-N(2)-C(10) 124.4(3)
C(9) - N(3)- C(13) 121.7(3) C(9)-N(3)-Li(1) 89.6(3)
C(13)-N(3)-Li(1) 146.1(3) N(3)-C(9)-N(1) 115.4(3)
N(3)-C(9)-N(2) 122.3(3) N(1) - C(9)-N(2) 122.2(3)
35
1丄
C26
Table 2-4. Selected bond lengths (A) and angles ( 0 ) of compound 5.

[Li(L3)(TMEDA)]
Li(1)-N(3) 1.984(5) Li(1)-N(1) 2.014(5)
Li(1)-N(5) 2.114(6) Li(1)-N(4) 2.140(5)
Si(1)-N(2) 1.736(2) N(1)-C(9) 1.340(3)
N(1)-C(1) 1.404(3) N(2)-C(9) 1.453(3)
N(2)- C(10) 1.485(3) N(3)-C(9) 1.315(3)
N(3)- C(19) 1.445(3)
N(3)-Li(1)- N(1) 68.4(1) N(3)—Li ⑴ - N ( 5 ) 118.0(3)
N(1)-Li ⑴ 一 N(5) 127.7(3) N(3)-Li(1)-N(4) 131.6(3)
N(1)-Li(1)-N(4) 131.4(3) N(4)-Li(1)-N(5) 85.7(2)
C(9)"N(1)- C(1) 123.0(3) C(9)-N(1)-Li(1) 87.1(2)
C(1)-N(1)-Li(1) 148.2(2) C(9)-N(2)-C(10) 113.2(1)
C(9)-N(3)-C(19) 121.8(2) C(9)-N(3)-Li(1) 89.0(2)
C(19)-N(3)-Li(1) 144.9(2) C(9)—N(2pSi(1) 123.4(6)
C(10)-N(2)-Si(1) 123.4(1)
36
2.3.1.2.1 Synthesis of Solvated Lithium Guanidinate [Li(L 1 )(THF)] 2 (6)
The synthetic pathway for the TMEDA-free lithium guandinate 6 is
illustrated in Scheme 2-7. Compound 6 was prepared by reacting CyN=C=NCy
with the lithium salt of 2,6-dimethylaniline in THF. The latter was prepared in
situ by reacting 2,6-dimethylaniline with UBu n in the absence of TMEDA. A
dimeric compound 6 was obtained as colorless crystals in 72% yield.
\ 、、N /
II I . L i B u " , THF, r.t.,8h w Cy / ^ \

^ H\ N,, I Cy H
2 2. C y N C N C y , T H F , r.t., 8h N — < N ^ L i
6 (72%)
b
Scheme 2-7
2.3.1.2.2 Physical Characterization of Compound 6
Compound 6 was characterized by 1H and 13 C NMR spectroscopy,
melting-point measurement, elemental analysis and X-ray crystallography. Its
1H NMR spectrum shows one set of resonance signals corrseponding to the L1
ligand and a THF molecule. Table 2-5 summarizes some physical properties of
the dimeric compound 6.
Table 2-5 Physical properties of compound 6.

Compound Yield (%) Appearance of Crystals M.p.《。C)
... 一一....一一一；：；； .... •
37
2.3.1.2.3 Molecular Structure of Compound 6
Good quality crystals of complex 6 suitable for X-ray diffraction study was
obtained from THF. Figure 2-4 shows the molecular structure of complex 6 with
the atom numbering scheme. Selected bond lengths and angles of compound
6 are listed in Table 2-6.
The binulear compound 6 crystallizes in the monoclinic crystal system with
the space group P2、lc. Each lithium atom is coordinated by two nitrogen atoms
(N(1) and N(3)) from a chelating L 1 ligand and one oxygen atom from a THF
solvent molecule. The N(3) atom is also coordinated to Li(1)，，forming a
dimeric structure and giving a distorted tetrahedral coordination environment
around the lithium center. The structure of compound 6 is different from that of
[Li(THF){M-(NBu02C(HNBu0}2Li].7 The two lithium atoms in the latter complex
exhibit a different coordination environment. The guanidinate ligand in the latter
complex was not binding in a chelating fashion.
The N(1)-Li(1)-N(3) bite angle of the guanidinate ligand in the compound
6 is 65.0(1)°，which is comparable to that in compound 1.
38
o rx
Figure 2-4. Molecular structure of [Li(L1)(THF)]2— (6) (30% thermal ellipsoids).
,•
[Li(L 1 )(THF)] 2
Li(1 ) - 0 ( 1 ) 2.013(5) Li(1)-N(1) 2.020(5)
Li(1)-N(3) 2.183(6) N(1)-C(9) 1.333(3)
N(1)-C(1) 1.395(3) N(2)-C(9) 1.381(3)
N(2)-C(10) 1.456(4) N(3)-C(9) 1.330(3)
N(3)-C(16) 1.469(4) N(3)-Li(1) 5 2.071(5)
0(1HJ(1)~N(1) 113.6(2) 0(1)-Li(1)-N(3)' 120.8(2)
N(1)-Li(1)-N(3)， 117.7(3) 0(1)-Li(1)-N(3) 120.2(3)
N(1)-Li(1)-N(3) 65.0(1) N(3)'-Li(1)-N(3) 107.0(2)
C(9)-N(1)-C(1) 125.4(2) C(9)-N(1)-Li(1) 91.1(2)
C(1)-N(1)-Li(1) 141.9(2) C(9)-N(2)-C(10) 125.6(2)
C(9)-N(3)-C(16) 121.6(2) C(9)-N(3)-Li(1)' 120.2(2)
C(16)-N(3)-Li(1)' 112.5(2) C(9)-N(3)-Li(1) 84.3(2)
C(16)-N(3)-Li(1 )， 136.1 (2) Li(1 ，

) 一 N(3)~Li(1) 73.0(2)
N(3)-C(9)-N(1) 116.3(2) N(3)-C(9)-N(2) 122.0(3)
N(1)-C(9)-N(2) 121.6(2)
39
2.3.2 S y n t h e s i s a n d S t r u c t u r e s of Manganese(ll) Bis(guanidinate)
Complexes
2.3.2.1 S y n t h e s i s of Manganese(ll) Bis(guanidinate) C o m p l e x e s
S u p p o r t e d by L n {n = 1 - 3 )
Manganese(ll) bis(guanidinate) complexes 7 - 9 supported by L n (n = 1 -
3) have been prepared by metathesis reaction of anhydrous manganese(ll)
chloride with two equivalents of the appropriate lithium guanidinates [Li(L n )
(TMEDA)] in a suitable solvent (Scheme 2-8).
H-N
I 1 U
/ -泊
/ 7 (58%)
/
/ H-N Y \ N-H
/ E t 2 0 , r. t., 8 h , ^ I \ /
u_
叫 + _ _ ^ 0 + 、 N 〜 N 、 — < 二
\ -
\
/x
x^r
\ 8 (50%)
\ 、今
\ Et20)r.t.,8h M63S \ , % 尸y
Xy
Cy J N SiMe 3
cy
9 (57%)
Scheme 2-8
Complexes 7 and 8 were isolated as pale yellow crystals in 58% and
50% yield (based on MnCb used), respectively. A small amount of THF is
required to promote the crystallization of complex 7. Both 7 and 8 are highly
40
soluble in diethyl ether，toluene and hexane. Compound 9 was obtained as
pink crystals in 57% yield. As complex 9 has a very low solubility in diethyl
ether, toluene was used to extract the product.
2.3.2.2 Physical Characterization of Compounds 7-9
The solid-state structures of compounds 7 - 9 were characterized by the
single-crystal X-ray diffraction. They were also characterized by melting-point
determination, magnetic moment measurement and elemental analysis.
Results of elemental analysis are consistent with their empirical formula. The
solution magnetic moments of compounds 7 and 8 are consistent with the
spin-only value of 5.92 |JB for a high-spin d 5 electronic configuration. The
solution magnetic moment of 4.24 |JB/ Mn(ll) ion for 8 is slightly lower than the
spin-only value. This may be attributed to the presence of an equilibrium
between monomer and dimer in the solution state. Table 2-7 lists some
physical properties of compounds 7 - 9 .
Table 2-7. Physical properties of compounds 7-9.

Compound Yield (%) Magnetic Appearance of M.p. (°C)
Moment (|IB> Crystals
7 58 5.55 Pale Yellow 130-132 (dec.)
8 50 4.24 / per Pale Yellow 104-106

Mn(ll) ion
9 57 5.67 Pink 113-115
41
2.3.2.3 Molecular Structures of Compounds 7-9
a. Molecular Structure of Compound 7
X-Ray quality crystals of compound 7 were obtained from toluene.
Figure 2-5 illustrates the molecular structure of compound 7 with the atom
numbering scheme. Selected bond lengths and angles are summarized in
Table 2-8.
The mononuclear compound 7 crystallizes in the monoclinic crystal
system with the space group P2"n. The manganese atom is five-coordinated
with a distorted trigonal bipyramidal geometry. The manganese center is
surrounded by two chelating guanidinate ligands and one THF solvent
molecule. The nitrogen atoms (N(1) and N(4)) occupy the axial positions. The
N(1)-Mn(1)-N(4) angle is 158.8(1)°. The equatorial plane is formed by 0(1)，
N(3) and N(6) with the sum of bond angles around the manganese center
being 360 0 . Owing to a restriction of the NCN backbone of the guanidinate
ligand, the trigonal bipyramidal geometry is highly distorted. As a result, the
axial nitrogen atoms are not perpendicular to the equatorial plane (N(4)-
Mn(1 ) - 0 ( 1 ) = 101.3(1)°, N(4)-Mn(1)-N(3) = 112.2(1)° and N(4)-Mn(1)-N(6)=
61.6(1)°). The axial bonds Mn(1)-N(1) (2.218(3) A) and Mn(1)-N(4) (2.212(3)
A) are slightly longer than the equatorial bonds Mn(1)-N(3) (2.130(3) A) and
Mn(1)-N(6) (2.131(3) A). This may be attributed to a stronger steric interaction
experienced by the two axial nitrogen atoms (N(1) and N(4)).
42
Figure 2-5. Molecular structure of [Mn(L 1 ) 2 (THF)] (7) (30% thermal ellipsoids).
. •r 、• •
‘ ；, ；
•
“ iUn{VWH¥)\
• “ ：
；：
-
钩麵‘：崎
： • • •
》〜，；
Mn(1)-N(3) 2.130(3) Mn(1)-N(6) 2.131(3)
Mn(1 ) - 0 ( 1 ) 2.168(3) Mn(1)-N(4) 2.212(3)
Mn(1)-N(1) 2.218(3) C(1)-N(1) 1.405(5)
C(9)-N(3) 1.325(4) C(9)-N(1) 1.344(5)
C(9)-N(2) 1.382(4) C(10)-N(2) 1.461(4)
C(16)-N(3) 1.450(5) C(22)-N(4) 1.414(5)
C(30)-N(6) 1.325(5) C(30)-N(4) 1.334(5)
C(30)-N(5) 1.380(5) C(31)- N(5) 1.462(5)
C(37)-N(6) 1.453(5)
N(3)-Mn(1)-N(6) 146.7(1) N(3)-Mn(1 ) - 0 ( 1 ) 105.3(1)
N(6)-Mn(1 ) - 0 ( 1 ) 108.0(1) N(3)-Mn(1 )-N(4) 112.2(1)
N(6)-Mn(1)-N(4) 61.6(1) 0(1)- Mn(1)-N(4) 101.3(1)
N(3)-Mn(1)-N(1) 61.9(1) N(6)- Mn(1)—N(1) 111.0(1)
0(1)-Mn(1)-N(1) 99.9(1) N(4HVIn(1)-N(1) 158.8(1)
43
N(3)-C(9)-N(1) 114.0(3) N(3)-C(9)-N(2) 122.2(3)
N(1 )-C(9)-N(2) 123.9(3) N(6)-C(30)-N(4) 113.6(3)
N(6hC(30)-N(5) 122.4(3) N(4)-C(30)- N(5) 123.9(3)
C(9)-N(1)-C(1) 123.9(3) C(9)-N(1)-Mn(1) 89.6(2)
C(1)一 N(1)-Mn(1) 134.1(2) C(9)-N(2)-C(10) 124.9(3)
C(9)一 N(3) - C(16) 124.9(3) C(9)-N(3)-Mn(1) 94.0(2)
C(16)-N(3)-Mn(1) 141.1(2) C(30)-N(4)-C(22) 124.3(3)
C(30)-N(4)-Mn(1) 90.3(2) C(22)-N(4)-Mn(1) 132.8(2)
C(30)-N(5)-C(31) 124.8(3) C(30)-N(6)-C(37) 124.5(3)
C(30)-N(6)-Mn(1) 94.1(2) C(37)-N(6)-Mn(1) 141.4(3)
44
b. Molecular Structure of Compound 8
Good quality crystals of compound 8 suitable for X-ray diffraction
analysis were obtained from diethyl ether. Figure 2-6 shows the molecular
structure of compound 8 with the atom numbering scheme. Selected bond
lengths and angles are listed in Table 2-9.
Compound 8 is a binuclear complex which crystallizes in the triclinic
crystal system with the space group P1. Each manganese atom is five-
coordinated by four nitrogen atoms of two chelating guanidinate ligands and
one nitrogen atom from a bridging TMEDA ligand. The coordination geometry
around the manganese atom can be described as distorted trigonal
bipyramidal. The nitrogen atoms (N(1) and N(4)) occupy the axial positions
with the N(1)-Mn(1)-N(4) angle of 153.1(1)°. The equatorial plane is formed by
N(3) g uanidinate, N(6) g U anidinate and N(7)TMEDA with the sum of angles around the
manganese center being 360 0 . The axial bonds Mn(1)-N(1) (2.228(3) A ) and
Mn(1)-N(4) (2.233(3) A) are slightly longer than the equatorial bonds Mn(1)-
N(3) (2.146(3) A ) and Mn(1)-N(6) (2.152(3) A ) . Both the axial and equatorial
M n - N bonds in compound 8 are slightly longer than those in the compound 7，
probably due to the more bulky TMEDA ligand in 8 as compared to THF in 7.
A similar structure has been observed in the manganese(ll)
bis(amidinate) [{Mn{n2-PhC(NSiMe3KNC6H3Me2-2，6)}2}2(TMEDA)].16 The Mn-N
bond lengths and N - M n - N bite angles of compound 8 (2.146(3) 一 2.238(3) A
and 61.6(1) 一 61.9(1)°) are comparable to those of 2.177(3) - 2.223(3) A and
61.58(9) — 61.97(9)。in [{Mn{r|2-PhC(NSiMe3)(NC6H3Me2-2，6)}2}2(TMEDA)].
45
C27 ^ L S ^
稱
Figure 2-6. Molecular structure of [{Mn(L 2 ) 2 } 2 (TMEDA)] (8) (30% thermal
ellipsoids).
_(L2)2}2(TMEDA)J
Mn(1)-N(3) 2.146(3) Mn(1)- N(6) 2.152(3)
Mn(1)-N(4) 2.223(3) Mn(1)-N(1) 2.238(3)
Mn(1)一 N(7) 2.302(4) N(1 )-C(9) 1 . 3 5 1 (5)
N(1 )-C(1) 1.413(5) N(2)-C(9) 1.379(5)
N(2)- C(10) 1.466(5) N(3)-C(9) 1.310(5)
N(3)- C(13) 1.461(5) N(4)-C(24) 1.345(5)
N(4)- C(16) 1.418(5) N(5)-C(24) 1.372(5)
N(5)- C(25) 1.457(6) N(6)-C(24) 1.331 (5)
N(6)-C(28) 1.479(6)
N(3)-Mn(1)一 N(6) 149.3(1) N(3)—Mn(1)- N(4) 107.5(1)
N(6)-Mn(1 )-N(4) 61.9(1) N(3)-Mn(1 )-N(1) 61.6(1)
N(6)-Mn(1 )-N(1) 113.7(1) N(4)- Mn(1 )-N(1) 153.1(1)
N(3)-Mn(1 )-N(7) 108.8(1) N(6)-Mn(1 )-N(7) 101.8(1)
46
N(4)-Mn(1 )-N(7) 102.7(1) N(1 )-Mn(1)- N(7) 104.1(1)
C(9)-N(1)一 C(1) 121.8(3) C(9)-N(1) Mn(1)

一 88.9(2)
C(1)-N(1)-Mn(1) 135.1(3) C(9)-N(2)-C(10) 124.8(3)
C(9)- N(3)-C(13) 121.5(3) C(9)-N(3)-Mn(1) 94.0(2)
C(13hN(3)- Mn(1) 144.3(3) C(24)-N(4)- C(16) 119.7(3)
C(24)-N(4)-Mn(1) 89.9(2) C(16)-N(4)-Mn(1) 134.9(2)
C(24)-N(5)-C(25) 125.2(4) C(24)-N(6)-C(28) 120.9(4)
C(24)-N(6)-Mn(1) 93.4(2) C(28)-N(6)-Mn(1) 145.7(3)
N(3)—C(9hN(1) 115.1(3) N(3)-C(9)-N(2) 123.1(4)
N(1)-C(9)-N(2) 121.7(3) N(6)-C(24)-N(5) 114.6(4)
N(6)-C(24)-N(5) 123.1(4) N(4)- C(24)-N(5) 122.3(4)
47
c. Molecular Structure of Compound 9
X-Ray quality crystals of compound 9 were obtained from toluene.
Figure 2-7 displays the molecular structures of compound 9 with the atom
numbering scheme. Selected bond lengths and angles are illustrated in Table
2-10.
The mononuclear compound 9 crystallizes in the triclinic crystal system
with the space group P I . The manganese atom is chelated by two guanidinate
ligands, displaying a distorted tetrahedral geometry. Compound 9 is four-
coordinated, whereas compounds 7 and 8 are five-coordinated. The
coordination number around the metal center is determined by the bulkiness of
the ligands. The more bulky ligand environment results in a smaller
coordination number. The presence of the -SiMe3 substituent has increased
the steric bulkyness of L 3 . For this reason, the coordination number of
compound 9 is lower than those of compounds 7 and 8.
The Mn-N bond distances in compound 8 (2.088(3) 一 2.109(3) A ) are
slightly shorter than those of 2.101(3) 一 2.123(3) A in the manganese(ll)
amidinate [Mn{n2-Ph(CNC6H3Pr/2-2J6)2}2].18 It is because the N-substituted aryl
group in the amidinate compound is sterically more bulky than that in
compound 8.
48
C2B C39
Figure 2-7. Molecular structure of [Mn(L3)2] (9) (30% thermal ellipsoids).
Table 2-10. Selected bond lengths ( A ) and angles (°) of compound 9.
[Mn(L3)2]
Mn(1)- N(3) 2.088(3) Mn(1)-N(6) 2.089(3)
Mn(1)-N(4) 2.105(3) Mn(1)-N(1) 2.109(3)
Si(1)-N(2) 1.758(3) Si(2)-N(5) 1.756(3)
N(1)-C(9) 1.348(4) N(1)-C(1) 1.412(5)
N(2)-C(9) 1.411(4) N(2)-C(13) 1.497(5)
N(3)-C(9) 1.330(4) N(3)-C(19) 1.445(5)
N(4)- C(33) 1.344(5) N(4) - C(25) 1.412(5)
N(5)-C(33) 1.420(4) N(5)-C(37) 1.501(5)
N(6)-C(33) 1.329(5) N(6)-C(43) 1.453(5)
N(3)-Mn(1)-N(6) 155.3(1) N(3)-Mn(1)-N(4) 128.3(1)
N(6)- Mn(1)—N(4) 63.9(1) N(3)-Mn(1)-N(1) 64.1(1)
N(6)-Mn(1)-N(1) 125.9(1) N(4)-Mn(1)-N(1) 134.8(1)
49
C(9) 一 N(1) - C(1) 124.8(3) C(9)一 N(1)- Mn(1) 90.9(2)
C(1)一 N(1 )-Mn(1) 139.9(3) C(9)-N(2)-C(13) 114.0(3)
C(9)-N(2)-Si(1) 123.7(2) C(13)-N(2)-Si(1) 121.9(3)
C(9)-N(3)-C(19) 124.9(3) C(9)-N(3)-Mn(1) 92.4(2)
C(19)一 N ⑶ 一 Mn(1) 132.1(2) C(33)- N(4)- C(25) 127.5(3)
C(33)-N(4)-Mn(1) 91.3(2) C(25)-N(4)-Mn(1) 137.0(2)
C(33)-N(5)-C(37) 113.4(3) C(33)-N(5)-Si(2) 123.4(2)
C(37hN(5)—Si(2) 123.1 (3) C(33)-N(6)-C(43) 124.7(3)
C(33)-N(6)-Mn(1) 92.4(2) C(42)-N(6)-Mn(1) 131.3(3)
N(3)-C(9)-N(1) 112.6(3) N(3)- C(9)一 N(2) 124.2(3)
N(1)-C(9)- N(2) 123.2(3) N(3)-C(9)-Mn(1) 55.8(1)
N(”-C(9hMn(1) 56.8(1) N(2)-C(9)- Mn(1) 177.1(3)
N(6)-C(33)-N(4) 112.2(3) N(6)-C(33)-N(5) 124.8(4)
N(4)—C(33)- N(5) 123.0(3) N(6)-C(33)-Mn(1) 55.8(1)
N(4)-C(33)-Mn(1) 56.5(1) N(5)-C(33)-Mn(1) 174.5(2)
50
2.3.3 Synthesis and Structures of Iron(ll) Bis(guanidinate) Complexes
2.3.3.1 Synthesis of Iron(ll) Bis(guanidinate) Complexes Supported by
L" (n = 2，3)
Iron(ll) bis(guanidinate) complexes 10 and 11 supported by L n (n = 2，3)
were synthesized by metathesis reactions of FeCb with two molar equivalents
of the appropriate lithium guanidinate (Scheme 2-9).
� $
Toluene，r. t.’ 8 h H\ N \ 、、N P—
/ - ^ �
\
/ 10 (50%)
FeCI 2 + 2 equiv [Li(L n )(TMEDA)] 1
M
\ — T i > < K
"=3 Cy N N siMe3
c y
11 (81%)
Scheme 2-9
The bis(guanidinate) iron(ll) compounds 10 and 11 were isolated as
pale yellow and green crystals, respectively. As compound 10 is highly soluble
in toluene and diethyl ether, hexane or pentane was employed for
crystallization of the compound. Attempts to prepare an iron(ll) derivative of the
L 1 ligand were unsuccessful. Only an intractable green oily liquid was obtained.
Addition of THF to the resultant mixture could not promote crystallization of the
desired product.
51
2.3.3.2 Physical Characterization of Compounds 10 and 11
Compounds 10 and 11 were characterized by melting-point
determination, magnetic moment measurement, elemental analysis, and X - r a y
crystallography. The solution magnetic moments of complexes 10 and 11 are
consistent with the spin-only values of 4.90 |JB for a high-spin d 6 electronic
configuration. Some physical properties of compounds 1 0 and 11 are listed in
Table 2-11.
Table 2-11. Physical properties of compounds 10 and 11.
crystals
10 50 4.98 Pale Yellow 198-200 (dec)
11 81 4.89 Green 200-202 (dec)
2.3.3.3. Molecular Structures of Compounds 10 and 11
Crystals of compounds 1 0 and 11 suitable for X-ray diffraction were
obtained from hexane and diethyl ether, respectively. The molecular structures
of complexes 10 and 11 with the atom numbering schemes are depicted in
Figures 2-8 and 2-9. Selected bond lengths and angles of compounds 1 0 and
11 are listed in Tables 2-12 and 2-13，respectively.
Compound 10 crystallizes in the monoclinic crystal system with the
space group C2/c，while compound 11 crystallizes in the triclinic crystal system
with the space group PT. Both compounds are mononuclear and isostructural.
They show a distorted tetrahedral coordination geometry around the metal
center. Two guanidinate ligands coordinate to the iron center in a chelating
manner. The coordination environment of 10 and 11 is different from that of the
52
first reported homoleptic iron(ll) bis(guanidinate) complexes [Fe{|j-n 2 -
(RN) 2 C(HNR)}{n 2 -(RN) 2 C(HNR)}] 2 (R = Cy, Pr'),9 which are binuclear
compounds. The guanidinate ligands in the latter complexes bond to the Fe(ll)
center in both chelating and bridging fashions. The observed Fe(1)-N(1) and
Fe(1)-N(3) bond distances in the compounds 1 0 and 11 cover the range of
2.049(1) 一 2.051(2) A and 2.011(1) - 2.032(2) A. The N(1)-Fe(1)-N(3) bite
angles of compounds 10 and 11 are 66.14(7)° and 65.40(9) 一 65.46(8)。，
respectively. The Fe-N bond distances in 10 and 11 are slightly shorter than
those of 2.112(3) - 2.134(2) A in [Fe{|j-n2-(CyN)2C(HNCy)}{n2-
(CyN)2C(HNCy)}]2，9 but comparable to those of 2.033(1) A in [Fe{q 2 -
CBuN) 2 CMe} 2 ]. 11 The N - F e - N bite angles (66.14(7)。for 10 and 65.40(9) 一
65.46(8)° in 11) are comparable to those of 63.07(9) 一 63.09(10)° in [Fe{[>n 2 -
(CyN)2C(HNCy)}{n2-(CyN)2C(HNCy)}]2,9 and 65.52(4)° in [Fe{r|2-(伯uN)2CMe}2].
11
The slightly longer Fe-N bond distances in 11 as compared to those in
the analogous compound 10 may be ascribed to a more bulky nature of the L 3
ligand. The observed M-N g U anidinate bond distances of the iron(ll) compound 11
(2.011(1) 一 2.032(2) A) are comparable to those of the manganese(ll)
analogue 9 (2.088(3) 一 2.109(3) A).
53
Figure 2-8. Molecular structure of [Fe(L 2 ) 2 ] ( 1 0 ) (30% thermal ellipsoids).
[Fe(L 2 ) 2 ]
Fe(1)-N(3) 2.011(1) Fe(1)— N(3)， 2.011(1)
Fe(1)-N(1)， 2.049(1) Fe(1)- N(1) 2.049(1)
N(1)-C(9) 1.347(3) N(1)-C(1) 1.412(3)
N(2)-C(9) 1.362(3) N(2)-C(10) 1.465(3)
N(3)- C(9) 1.331(3) N(3)- C(13) 1.460(3)
N(3)-Fe(1 )-N(3), 144.0(1) N(3)-Fe(1)- N(1 )， 129.0(7)
N(3)，一 Fe(1 )-N(1 )， 66.14(7) N(3)-Fe(1 )-N(1) 66.14(7)
N(3)，一 Fe(1 )-N(1) 129.0(7) N(1 )，一 Fe(1) - N(1) 137.3(1)
C(9)-N(1)-C(1) 126.3(1) C(9)-N(1)-Fe(1) 90.0(1)
C(1)-N(1)-Fe(1) 137.1(1) C(9)-N(2)-C(10) 124.8(1)
C(9)-N(3)-C(13) 123.4(1) C(9)-N(3)-Fe(1) 92.2(1)
C(13)-N(3)-Fe(1) 143.8(1) N(3)-C(9)-N(1) 111.6(1)
N(3)-C(9)-N(2) 123.8(1) N(1)- C(⑴-N(2) 124.6(1)
54
C40
Figure 2-9. Molecular structure of [Fe(L3)2] (11) (30% thermal ellipsoids).
[Fe(L 3 ) 2 ]
Fe(1)-N(6) 2.026(2) Fe(1)- N(3) 2.032(2)
Fe(1)-N(4) 2.049(2) Fe(1)-N(1) 2.051(2)
Si(1)- N(2) 1.757(2) Si(2)-N(5) 1.746(3)
N(1)-C(9) 1.342(3) N(1)- C(1) 1.426(3)
N(2)-C(9) 1.416(3) N(2)-C(13) 1.494(3)
N(3)-C(9) 1.328(3) N(3)- C(19) 1.459(3)
N(4)-C(33) 1.332(4) N(4)-C(25) 1.428(4)
N(5)- C(33) 1.417(3) N(5)-C(37) 1.490(4)

N(6)-C(33) 1.330(3) N(6)-C(43) 1.458(4)
N(6)- Fe(1)-N(3) 118.80(9) N(6)-Fe(1)-N(4) 65.40(9)
N(3)-Fe(1)-N(4) 147.8(1) N(6)-Fe(1)-N(1) 151.4(1)
N(3)-Fe(1)-N(1) 65.46(8) N(4)-Fe(1)-N(1) 127.85(9)
C (9)-N(1)-C(1) 123.5(2) C(9)-N(1)-Fe(1) 90.9(1)
55
C(1)一 N(1 hFe(1) 142.2(1) C(9)-N(2)-C(13) 113.5(2)
C(9)-N(2)-Si(1) 122.7(1) C(13)-N(2)-Si(1) 123.7(1)
C(9)-N(3)-C(19) 124.8(2) C(9)-N(3)-Fe(1) 92.1(1)
C(19)- N(3) - Fe(1) 138.8(1) C(33)-N(4)-C(25) 124.4(3)
C(33)-N(4)-Fe(1) 91.0(1) C(25)—N(4)- Fe(1) 141.5(2)
C(33)-N(5)-C(37) 113.7(2) C(33)-N(5)-Si(2) 123.0(2)
C(37)-N(5)-Si(2) 123.2(1) C(33)-N(6)-C(43) 123.3(2)
C(33)-N(6)-Fe(1) 92.0(1) C(43) - N(6)-Fe(1) 138.1(1)
N(3)-C(9)-N(1) 111.5(2) N(3)-C(9)-N(2) 124.5(2)
N(1)-C(9)-N(2) 124.0(2) N(6)-C(33)-N(4) 111.5(2)
N(6)-C(33)-N(5) 123.7(3) N(4)-C(33)-N(5) 124.7(3)
56
2.3.4 Synthesis and Structures of Cobalt(ll) Bis(guanidinate) Complexes
2.3.4.1 Synthesis of Cobalt(ll) Bis(guanidinate) Complexes Supported
by L" (n = 1 - 3 )
CobaK(ll) bis(guanidinate) complexes 12-14 were prepared by
metathesis reaction of cobalt(ll) chloride with two molar equivalents of the
lithium salts of L n (n = 1 - 3 ) in diethyl ether (Scheme 2-10).
R' N N R
Et20, r. t., 8 h \ 々 \ /
CoCI2 + 2 equiv [Li(Ln)(TMEDA)] N~(( Co ))~N
n = 1-3 / \〉Z、、、J 、
J N N r’
• V \
12 L1 : R = Cy, R' = H (70%)
13L2:R = PR 1，R'= H (80%)
14L :R = Cy, R' = SiMe3 (70%)
3
Scheme 2-10
Compounds 12 and 13 were isolated as violet crystals from diethyl ether
in 80% and 70% yield, whereas compound 14 crystallized as brown crystals in
70% yield from 1:3 diethyl ether/toluene.
Compounds 12-14 were characterized by X-ray crystallography,
melting-point determination, magnetic moment measurement, and elemental
analysis. Results of elemental analysis were consistent with the empirical
formula of the three compounds. The solution magnetic moments of
compounds 12-14 were found to be 5.38 (JB, 5.00 [JB and 4.89 |JB, respectively.
These values deviate from the spin-only value of 3.87 |jb for a high-spin d 7
57
electronic configuration for Co(ll). This may be attributed to spin-orbit coupling.
17 Table 2-14 depicts some physical properties of compounds 12，13 and 14.

Compound Yteld (%) Magnetic Appearance o f (°C)
Moment (\XB) Crystals
..:.::..….....:r"......(二……:....... ： . . … � ‘ 一 / 4, ¾ ¾ ¾ ¾ ^ ^ ^ $ 1 ¾ ^ ¾ ¾ ^ ¾ ¾ ^ ¾ ¾ ¾ ¾ ^ ^ ¾ ¾ ¾ ¾ ¾ ¾ 1 ¾ ¾ ^ ^ ¾ ^ ¾ ^ ¾ 感慮
12 70 5.38 Violet 150-152
13 80 5.00 Violet 104-106
14 70 4.89 Brown 164-165
Good quality crystals of complexes 12-14 suitable for X-ray diffraction
studies were obtained from diethyl ether (12 and 13) and a mixture of diethyl
ether/toluene (14). The molecular structures of compounds 12-14 with the
atom numbering scheme are presented in Figures 2-10，2-11 and 2-12,
respectively. Selected bond lengths and angles are listed in Tables 2-15，2-16
and 2-17.
a. Molecular Structures of Compounds 12 and 13
The mononuclear compound 12 crystallizes in the monoclinic crystal
system with the space group C2/c，whereas compound 13 crystallizes in the
triclinic crystal system with the space group P1. Compounds 12 and 13 are
isostructural. Both complexes adopt a distorted tetrahedral coodination
geometry. The cobalt(ll) center is bound by two guanidinate ligands. The
observed Co-N bond lengths of 12 and 13 cover the range of 1.979(4) 一
2.018(4) A and 1.984(2) 一 2.030(2) A. The N—Co-N bite angles of 12 and 13
fall within the range of 6 6 . 7 ( 1 ) - 66.9(1)° and 66.57(9)°, respectively. The Co-N
58
bond lengths and N - C o - N bite angles of the two compounds are comparable
to those of the analogous Co(ll) amidinate, [Co{n 2 -( f BuN) 2 CMe} 2 ] (2.012(8) A
and 65.57(6)�), 11[Co{n2-PhC(NC6H3Pr'2-2，6)2}2] (1.989(7) 一 2.029(6) A and
66.2(3) 一 66.4(3)°) 18 and [Co{n2-{2,6-(4-Bu^Ph)}2PhC(NPr/)2}2] (1.973(4) -
1.993(3) A and 65.9(2) 一 66.0(1)°). 19
59
C40
m
033
%
C25
Figure 2-10. Molecular structure of [Co(L 1 ) 2 ] (12) (30% thermal ellipsoids).
Co(1)- N(3) 1.979(4) Co(1)-N(6) 1.983(5)
Co(1)-N(1) 2.008(4) Co(1)-N(4) 2.018(4)

N(1)- C(9) 1.336(5) N(1)-C(1) 1.414(5)
N(2)-C(9) 1.351(6) N(2)-C(10) 1.462(6)
N(3)- C(9) 1.338(6) N(3)-C(16) 1.448(5)
N(4)-C(30) 1.358(6) N(4)-C(22) 1.402(5)
N(5)-C(30) 1.352(6) N(5)-C(31) 1.474(6)
N(6)-C(30) 1.324(6) N(6)-C(37) 1.425(7)
N(3)-Co(1)-N(6) 135.7(1) N(3)-Co(1)-N(1) 66.9(1)
N(6)-Co(1)-N(1) 135.2(1) N(3)-Co(1)-N(4) 141.3(1)
60
N(6)- Co(1 )-N(4) 66.7(1) N(1)一 Co(1 )-N(4) 124.0(1)
C(9)-N(1 ) 128.8(4) C(9)-N(1 )-Co(1) 90.7(3)
C(1 )-N(1 )-Co(1) 137.7(3) C(9)-N(2)-C(10) 125.6(4)
C(9)-N(3)-C(16) 124.2(4) C(9)-N(3)-Co(1) 91.9(3)
C(16)-N(3)—Co(1) 141.5(3) C(30)-N(4)-C(22) 126.5(4)
C(30)—N(4)- Co(1) 90.2(3) C(22)-N(4)-Co(1) 133.1(3)
C(30)-N(5)-C(31) 126.0(4) C(30)-N(6)-C(37) 125.2(5)
C(30)-N(6)-Co(1) 92.7(3) C(37)-N(6)-Co(1) 141.5(4)

N(1)-C(9)-N(3) 110.6(4) N(1 )-C(9)-N(2) 125.7(4)
N(3)-C(9)-N(2) 123.6(4) N(6)-C(30)-N(5) 124.4(5)
N(6)-C(30)-N(4) 110.3(4) N(5)-C(30)-N(4) 125.3(4)
61
Q
C15 I
en务
© C12
Figure 2-11. Molecular structure of [CoL 2 ) 2 ] (13) (30% thermal ellipsoids).
_ _ ... .... :. .: ...:.. [Co(L2)a]
Co(1)-N(3) 1.984(2) Co(1)-N(1) 2.030(2)

N(1)—C(9) 2.433(3) N(1)-C(1) 1.409(3)
N(2)- C(9) 1.357(3) N(2) - C(10) 1.462(4)
N(3)-C(9) 1.326(3) N(3)-C(13) 1.462(3)
N(3)- Co(1 )—N(3)， 143.2(1) N(3)- Co(1)- N(1 )， 129.05(9)
N(3)-Co(1 )-N(1 )， 66.57(9) N(1 )'-Co(1 )-N(1) 136.8(1)
C(9)一 N(1)- C(1) 126.5(2) C(9)-N(1)-Co(1) 89.9(1)
C(1)-N(1)-Co(1) 136.3(1) C(9)-N(2)-C(10) 124.4(2)

C(9)-N(3)-C(13) 123.9(2) C(9)-N(3)-Co(1) 92.4(1)
C(13)-N(3)-Co(1) 142.8(1) N(3)-C(9)-N(1) 111.1(2)
N(3)-C(9)-N(2) 124.0(2) N(1)-C(9)-N(2) 124.9(2)
62
b_ Molecular Structure of Compound 14
The homoleptic compound 14 crystallizes in the monoclinic crystal
system with the space group P2/Jn. The mononuclear compound 14 is found to
adopt a square planar geometry. The cobalt center is surrounded by two
guanidinate ligands which are binding in a chelating fashion. The angles of
N(1)-Co(1)-N(1)' and N(3)-Co(1)-N(3)，are 180°. The nitrogen atoms N(1)，
N(1)', N(3) and N(3)' form a plane around the cobalt center with the sum of
angles 360°. The 2,6-dimethylphenyl substituent of the L 3 ligand is orthogonal
to the guanidinate CN3 motif. This minimizes steric repulsion with the
cyclohexyl substituent on the opposite L 3 ligand of the same molecule. The
SiMe3 group and the cyclohexyl group attached to the uncoordinated nitrogen
have protected the central cobalt atom by occuping the apical space.
Square planar coordination of cobalt(ll) complexes are commonly found
in the preorganised tetradentate ligands, such as porphyrins and salen. 20
Square planar cobalt(ll) complexes with two chelating ligands are rare. 21 The
formation of the square planar cobalt(ll) compound 14 may be attributed to the
steric bulkiness of the L 3 ligand. It is believed that interligand interactions
between the two L 3 ligands on 14 force the cobalt(ll) ion to adopt a square
planar geometry, instead of an electronically favorable tetrahedral geometry. A
similar case has been reported in [Fe{r|2-PhC(NC6H3P"2-2，6)2}2]，18 in which the
iron(ll) center exhibits a distorted square planar geometry due to interligand
interactions.
63
h V f - ^ 3
w0 4
Figure 2-12. Molecular structure of [Co(L 3 ) 2 ] (14) (30% thermal ellipsoids).
[CO(L 3 )2]
Co(1)-N(1) 1.908(2) Co(1)-N(1)' 1.908(2)

Co(1)- N(3) 1.939(2) Co(1)-N(3)， 1.939(2)
Si(1)-N(2) 1.758(2) N(1)-C(9) 1.331(3)
N(1)-C(1) 1.414(3) N(2)-C(9) 1.408(3)
N(2)-C(10) 1.491(4) N(3)-C(9) 1.332(3)

N(3)-C(19) 1.456(3)
N(1 )-Co(1 )-N(1)’ 180.00(7) N(1)一 Co(1)- N(3) 68.24(9)
N(1 )，-Co(1 )-N(3) 111.76(9) N(1 )-Co(1 )-N(3)' 111.76(9)
N(1 )，—Co(1 )-N(3)， 68.24(9) N(3)-Co(1 )-N(3)， 180.0(1)
C(9) - N(1)—C(1) 127.1(2) C(9)-N(1)-Co(1) 92.4(1)

C(1)-N(1)-Co(1) 140.3(1) C(9)一 N(2)- C(10) 113.5(2)
C(9)-N(2)-Si(1) 121.2(1) C(10)-N(2)-Si(1) 125.4(1)
C(9)-N(3)-C(19) 121.9(2) C(9)-N(3)-Co(1) 91.0(1)

C(19)-N(3)-Co(1) 136.7(1) N(1)-C(9)-N(3) 108.3(2)
N(1)-C(9)-N(2) 125.6(2) N(3)-C(9)-N(2) 126.1(2)
64
2.3.5 Synthesis and Structures of Nickel(ll) Bis(guanidinate) Complexes
2.3.5.1 Synthesis of Nickel(ll) Bis(guanidinate) Complexes Supported
by L n ( n = 1, 2)
The nickel(ll) bis(guanidinate) complex 15 was synthesized by treating
NiCb with [Li(L 1 )(TMEDA)] (1) in diethyl ether. However, X-ray quality crystals
of 15 could not be obtained. The product was isolated as deep blue crystals,
which were contaminated with a white solid. The latter remained unidentified.
Therefore, a modified synthetic procedure was employed, as shown in Scheme
2-11. Compounds 15 and 16 were synthesized by reacting NiCbfTMEDA) with
two molar equivalents of [Li(L n )(TMEDA)] in THF. The NiCI 2 (TMEDA) complex
was prepared in situ by refluxing NiCb with an equimolar amount of TMEDA in
THF.
R' N N R
THF, r. t„ 8 h \ //^-. /
NiCI2(TMEDA) + 2 equiv [Li(Ln)(TMEDA)] N~U ))~N
n
“ = ‘'^
12 Rd K
N 、NJ R-\
15 L1 : R = Cy, R' = H (60%)

16L2:R = PR 1', R' = H (50%)
Scheme 2-11
Compounds 15 and 16 were isolated as deep blue crystals from diethyl
ether in 60% and 50% yield, respectively. Attempts to prepare the nickel(ll)
bis(guanidinate) derivative of the L 3 ligand were unsuccessful. Only a black
solid was isolated, which remained unidentified.
65
The molecular structures of compounds 15 and 16 were determined by
X - r a y crystallography. They were further characterized by 1 H and 13 C NMR,
melting-point measurement and elemental analysis. Compounds 15 and 16
are diamagnetic. Their 1 H NMR spectra showed one set of resonance signals
corresponding to the L 1 and L 2 ligands, respectively. Some physical properties
of compounds 15 and 16 are depicted in Table 2-18.

• • • 1 • . 1 • : , . 1 1 …1•,」 1 川11 ““ 1 I 1 1 “ ‘ • . ,
Compound Yield (%) Appearance of Crystals M.p, (。C)
15 60 Deep blue 202-205
16 50 Deep blue 160-162
2.3.5.3 Molecular Structures of Compounds 15 and 16
X-Ray quality crystals of compounds 15 and 16 were grown from hexane.
Their molecular structures with the atom numbering scheme are illustrated in
Figures 2-13 and 2-14，respectively. Selected bond distances and bond angles
of compounds 15 and 16 are shown in Tables 2-19 and 2-20.
Compound 15 crystallizes in the triclinic crystal system with the space
group PT, whilst compound 16 crystallizes in the monoclinic crystal system
with the space group C2/m. The homoleptic compounds 15 and 16 are
isostructural with a square planar geometry. The nickel center is bound by two
chelating guanidinate ligands. The angles of N(1)-Ni(1)-N(4) and N(3)-Ni(1)-
N(6) are 1800. A square planar structure is commonly observed for nickel(ll)
complexes with a 16-electron configuration. The Ni-N bond lengths of 15 and
16 fall in the range of 1.886(4) 一 1,943(4) A and 1.915(4) 一 1.950(4) A,
66
respectively. The N - N i - N bite angles of 15 and 16 are 68.9(1) 一 69.4(1)° and
68.5(1)°. The bond lengths and bite angles of the two compounds are
comparable to the those reported for the Ni(ll) amidinate complex [Ni{rj 2 -
PhC(NSiMe3)(NC 6 H 3 Me 2 -2，6)} 2 ] (1.908(2) 一 1.945(2) A and 68.93(7) 一
69.09(7) 0 ). 16 Examples of nickel(ll) amidinate complexes with distorted
tetrahedral geometry have also been reported. 18 ' 19 The Ni-N bond lengths and
N - N i - N bite angles of 15 and 16 are comparable to the tetrahedral [Ni{r|2-
PhC(NC6H3PrV2，6)2}2] (1.918(2) 一 1.9288(18) A and 68.63(8)°) 18 and [_ 2 -
{2，6-(4-Bu卩h)}2PhC(NPr')2}2] (1.969(3) 一 1.977(2) A and 66.1(1) 一 66.3(1 )°).19
67
- A
N»lKnb28
# .
Figure 2-13. Molecular structure of [Ni(L1)2] (15) (30% thermal ellipsoids).
Ni(1)-N(6) 1.886(4) Ni(1)-N(3) 1.896(4)

Ni(1)-N(4) 1.937(4) Ni(1)- N(1) 1.943(4)
N(1)-C(9) 1.345(6) N(1)-C(1) 1.424(6)
N(2)-C(9) 1.376(6) N(2)- C(10) 1.458(6)
N(3)-C(9) 1.308(6) N(3)-C(16) 1.363(6)

N(4)- C(30) 1.346(6) N(4)-C(22) 1.411(6)
N(5)-C(30) 1.356(6) N(5)- C(31) 1.467(6)
N(6)-C(30) 1.328(6) N(6)-C(37) 1.458(6)
N(6)-Ni(1)-N(3) 179.4(2) N(6)-Ni(1)-N(4) 69.4(1)
N(3)-Ni(1)-N(4) 111.0(1) N(6)-Ni(1)-N(1) 110.8(1)

N(3)-Ni(1)-N(1) 68.9(1) N(4)-Ni(1)-N(1) 179.8(1)
C(9)-N(1)-C(1) 121.4(4) C(9)-N(1)-Ni(1) 88.7(3)
C(1)-N(1)-Ni(1) 134.5(3) C(9)-N(2)-C(10) 123.3(4)
68
C(9)-N(3)-C(16) 124.7(5) C(9)-N(3)-Ni(1) 91.8(3)
C(16)-N(3)-Ni(1) 143.3(4) C(30)-N(4)-C(22) 123.4(4)

C(30)-N(4)-Ni(1) 88.7(3) C(22)- N(4)- Ni(1) 132.1(3)
C(30)-N(5)-C(31) 125.5(4) C(30)-N(6)-C(37) 123.8(4)
C(30)- N(6)- Ni(1) 91.4(3) C(37)—N(6)- Ni(1) 143.0(3)
N(1)-C(9)-N(1) 109.8(4) N(3)-C(9)-N(2) 126.2(5)

N(1)-C(9)-N(2) 124.0(4) N(6)-C(30)-N(4) 109.0(4)
N(6)-C(30)-N(5) 125.2(5) N(4)-C(30)-N(5) 125.8(5)
69
CM ^^06
Figure 2-14. Molecular structure of [Ni(L2)2] (16) (30% thermal ellipsoids).
Table 2-20. Selected bond distances (A) and angles (°) of compound 16.
[Ni(L 2 ) 2 ]
Ni(1)-N(3) 1.915(4) Ni(1)- N(1) 1.950(4)

N(1)-C(9) 1.351(6) N(1)- C ⑴ 1.412(6)
N(2)- C(9) 1.358(7) N(2)-C(10) 1.485(6)
N(3)-C(9) 1.318(6) N(3)-C(13) 1.479(6)
N(3)'-Ni(1 )-N(3) 180.00(9) N(3)'-Ni(1 )-N(1) 111.6(1)
N(3)- Ni(1)- N(1) 68.5(1) N(3)-Ni(1)- N(1), 111.6(1)

N(1)-Ni(1)- N(1)， 180.0(1) C(9)-N(1)-C(1) 123.4(4)
C(9)-N(1)-Ni(1) 88.5(3) C(1)-N(1)-Ni(1) 131.9(3)

C(9)-N(2)-C(10) 126.4(4) C(9)-N(3)-C(13) 121.7(4)
C(9)-N(3)-Ni(1) 91.0(3) C(13)-N(3)-Ni(1) 141.5(3)
N(3)-C(9)-N(1) 109.1(4) N(3)-C(9)-N(2) 125.0(4)
N(1)-C(9)-N(2) 125.9(4)
70
2.3.6 Synthesis and Structures of Bis(guanidinate) Complexes of the
Group 12 Metals (M = Zn, Cd)
2.3.6.1 Synthesis of Zn(ll) and Cd(ll) Bis(guanidinate) Complexes
Supported by L n (n = 1 - 3 )
Zinc(ll) and cadmium(ll) bis(guanidinate) complexes 17-20 were
prepared by the reactions of MCI2 (M = Zn, Cd) with two molar equivalents of
[Li(L")(TMEDA)] (n = 1-3)，as shown in Scheme 2-12.
R, N N R
E t 2 0 , r. t., 8 h \ I, \ . 、、、\
、 /
I Zn、)V-N
/ ^ ^ ^ r7 K 、厂 \R,
ZnCI 2 / \ J T
/ 1 7 L 1 : R = Cy, R ' = H ( 4 5 % )
/ 18 L 2 : R = Pr1, FT = H (46%)
2 equiv [Li(L")(TMEDA)] — / 19 P : R = Cy ，R, = SiMe 3 (24%)
p
C D C L \ R' Q r i
— ^ FV—NrC丨d 、 N ^ ^ N 、 C 丨d 、 N - P r '
H-N \ . x / N-H
pj Xf 20 (14%)
xir ‘
Scheme 2-12
The homoleptic zinc(ll) guanidinate compounds 17-19 and the binuclear
cadmium(li) guanidinate complex 20 were isolated as colorless crystals. For
compound 17，the reaction yield could be improved 45% to 64% by extending
the reaction time from 8 hours to 4 days. Compound 20 was found to be
relatively unstable at room temperature, even though the compound was
71
stored under nitrogen. The compound turned gradually from white to yellow
after standing at room temperature for several days. As both zinc(ll) and
cadmium(ll) ions have a d 10 electronic configuration, they are diamagnetic and
were characterized by 1 H and 13 C NMR.
Compounds 17-20 were characterized by X - r a y crystallography, 1 H and
13 C NMR, melting-point determination and elemental analysis. Some physical
properties are depicted in Table 2-21.

Compound Yield (%) Appearance of Crystals M.p. (°C)
17 45 Colorless 157-159
18 46 Colorless 115-117
19 24 Colorless 182-184 (dec)
20 14 Colorless 116-118
X-Ray quality crystals of complexes 17-20 were grown from diethyl ether.
The molecular structures of 17-20 with the atom numbering scheme are
illustrated in Figures 2-15，2-16，2-17 and 2-18，respectively. Selected bond
distances and bond angles for these compounds are presented in Tables 2-22，
2-23, 2-24 and 2-25.
72
a. Molecular Structures of Compounds 17-19
Complexes 17 and 18 crystallize in the triclinic crystal system with the
space group pT, and compound 19 crystallizes in the monoclinic crystal
system with the space group C2/c. They are isostructural and both compounds
exhibit a distorted tetrahedral gemetry. The zinc atom is coordinated by two
guanidinate ligands in a chelating manner. The Z n - N bond lengths of
compounds 17，18 and 19 are in the range of 1.983(4) - 2.066(4) A, 1 . 9 9 3 ( 1 ) -
2.050(1) A and 1.996(1) - 2.047(1) A and the N - Z n - N bite angles cover the
range of 66.2(1) 一 66.6(1)°，66.50(7)° and 66.19(7) - 66.51(7)。，respectively.
Their Z n - N bond distances and N - Z n - N bite angles are similar to those
reported for [Zn{n2-(Me3Si)2NC(NPri)2}2] (2.011(2) 一 2.021(2) A and 66.23(8)°)
and [Zn{n 2 -(Me 3 Si) 2 NC(NCy) 2 }2] (2.006(2) A and 66.23(8)°). 13 They are also
comparable to the homoleptic zinc(ll) amidinate [Zn{r|2-(Ph)2NC(H)}2]，
(2.031 (5) 一 2.038(4) A and 65.86(18)。).22
73
Figure 2-15. Molecular structure of [Zn(L1)2] (17) (30% thermal ellipsoids).
[Zn(L 1 ) 2 ]
Zn(1)-N(6) 1.980(3) Zn(1)-N(3) 1.983(4)
Zn(1)-N(1) 2.034(3) Zn(1)-N(4) 2.066(4)
N(1)-C(9) 1.335(5) N(1)-C(1) 1.408(5)
N(2)-C(9) 1.350(6) N(2)-C(10) 1.463(5)
N(3)-C(9) 1.320(6) N(3)-C(16) 1.70(1)
N(4) - C(30) 1.336(5) N(4)-C(22) 1.407(5)
N(5)-C(30) 1.365(6) N(5)-C(31) 1.461(6)
N(6)-C(30) 1.330(5) N(6hC(37) 1.444(5)
N(6)-Zn(1)-N(3) 138.3(1) N(6)-Zn(1)-N(1) 143.5(1)
N(3)-Zn(1)-N(1) 66.2(1) N(6)-Zn(1)-N(4) 66.6(1)

N(3)-Zn(1)-N(4) 133.4(1) N(1)-Zn(1)-N(4) 120.6(1)
C(9)-N(1)~C(1) 125.4(3) C(9)-N(1)-Zn(1) 89.8(2)
C(1)-N(1)-Zn(1) 132.4(3) C(9)-N(2)-C(10) 126.4(4)
74
C(9)-N(3)-C(16) 123.0(5) C(9) 一 N(3)-Zn(1) 92.5(3)
C(16)-N(3)-Zn(1) 144.3(4) C(30) - N(4)-C(22) 128.3(4)
C(30)-N(4)-Zn(1) 88.3(3) C(22)-N(4)-Zn(1) 139.0(3)
C(30)-N(5)-C(31) 125.9(4) C(30)-N(6)-C(37) 124.0(4)
C(30)-N(6) - Zn(1) 92.1 (3) C(37)-N(6)-Zn(1) 139.2(3)
N(3)-C(9)-N(1) 111.4(4) N(3)-C(9) - N(2) 123.5(4)
N(1) - C(9)-N(2) 125.0(4) N(6)-C(30)-N(4) 113.0(4)
N(6) - C(30)—N(5) 122.8(4) N(4) - C(30) - N(5) 124.1(4)
75
Figure 2-16. Molecular structure of [Zn(L2)2] (18) (30% thermal ellipsoids).
[Zn(L2)2]
Zn(1)-N(3) 1.993(1) Zn(1) - N(1) 2.050(1)
N(1 )-C(9) 1.348(3) N(1 )-C(1) 1.408(3)
N(2) - C(9) 1.364(3) N(2hC(10) 1.459(3)
N(3) - C(9) 1.325(3) N(3)-C(13) 1.462(3)
N ⑶，一Zn(1)-N(3) 143.3(1) N ⑶-Zn(1)-N(1) 66.50(7)
N ⑶ 一 Zn(1) - N(1 )， 129.65(8) N(1 )-Zn(1 )-N(1 )， 135.3(1)
C(9)-N(1)-C(1) 126.0(1) C(9)-N(1)-Zn(1) 89.2(1)

C(1)-N(1)-Zn(1) 136.7(1) C(9)-N(2) - C(10) 124.7(2)
C(9hN(3) - C(13) 124.0(2) C(9)-N(3)-Zn(1) 92.3(1)
C(13)-N(3)-Zn(1) 142.4(1) N(3)-C(9)-N(1) 112.0(1)
N(3)-C(9)-N(2) 123.8(2) N(1) - C(9)—N(2) 124.2(2)
76
C28 C27
“：|： w
Figure 2-17. Molecular structure of [Zn(L 3 ) 2 ] (19) (30% thermal ellipsoids).
[Zn(L 3 ) 2 ]
•
Zn(1)-N(3) 1.996(1) Zn(1)-N(6) 1.999(1)
Zn(1)-N(4) 2.037(1) Zn(1)-N(1) 2.047(1)
Si(1 )-N(2) 1 -755(1) Si(2)-N(5) 1.763(1)
C(9)-N(3) 1.333(2) C(9)-N(1) 1.348(3)
C(9)-N(2) 1.405(3) C(33) - N(6) 1.327(3)
C(33)-N(4) 1.343(3) C(33) - N(5) 1.406(3)
N(3) - Zn(1 )-N(6) 150.84(7) N(3)-Zn(1 )-N(4) 126.74(7)
N(6)-Zn(1 )-N(4) 66.19(7) N(3)-Zn(1 )-N(1) 66.51 (7)
N(6) - Zn(1 )-N(1) 125.54(7) N(4) - Zn(1)—N(1) 135.98(7)
N(3)-C(9)-N(1) 111-6(1) N(3)-C(9)-N(2) 124.7(1)
N(1 )-C(9)-N(2) 123.6(1) N(6)-C(33)-N(4) 111.3(1)
N(6)-C(33)-N(5) 125.3(1) N(4)-C(33)-N(5) 123.4(1)
C(9)-N(1 )-C(1) 124.7(1) C(9)-N(1 )-Zn(1) 89.6(1)
C(1 )-N(1 )-Zn(1) 140.6(1) C(9)-N(2)-C(10) 113.5(1)
77
C(9) - N(2) - Si(1) 113.6(1) C(10)-N(2) - Si(1) 122.7(1)
C(9)-N(3)-C(19) 125.0(1) C(9) - N ⑶ - Z n ( 1 ) 92.2(1)
C(19) 一 N(3) - Zn(1) 131.8(1) C(33)-N(4)-C(25) 126.1 (1)
C(33)-N(4)-Zn(1) 90.1(1) C 口 5)-N ⑷ - Z n ( 1 ) 138.1(1)
C(33) - N(5) - C(34) 113.4(1) C(33)-N(5)-Si(2) 123.5(1)
C(34)-N(5)-Si(2) 123.0(1) C(33)-N(6)-C(43) 124.8(1)
C(33) - N(6) - Zn(1) 92.2(1) C(43)-N(6)-Zn(10 131.0(1)
78
b. Molecular Structure of Compound 20
The binuclear compound 20 crystallizes in the triclinic crystal system with
the space group P1. Each cadmium atom is five-coordinated with a highly
distorted trigonal bipyramidal geometry. The cadmium atom is bound by two
chelating guanidinate ligands and one nitrogen atom from a bridging TMEDA
ligand. A similar molecular structure was also found in the binuclear
[{Mn(L 2 ) 2 } 2 (TMEDA)] (8). The nitrogen atoms (N(1) and N(4)) occupy the apical
positions with the N(1)-Cd(1)-N(4) bond angle of 147.6(1)°. The equatorial
plane are formed by N(3) g U anidinate, N(6)gUanidinate and N(7)TMEDA with an angle
sum of 360 0 around the cadmium center. The cadmium(ll) ion has a larger
ionic size than zinc(ll) ion. Therefore, the cadmium(ll) ion requires more bulky
ligand to stabilize its coordination sphere. The cadmium(ll) gaunidinate
compound 20 has a higher coordination number and longer M - N bond lengths
than those of the zinc(ll) guanidinate 18. The N guanidinate Cd-N guanidinate bite
一
angles are 58.3(1) 一 58.5(1)°, which are smaller than those of the other
bis(guanidinate) complexes reported in this work. It even falls outside the
range of 64 一 68° generally observed for the bite angles in other guanidinate
compounds. 1 ' 2
79
W ¥
Figure 2-18. Molecular structure of [{Cd(L 2 ) 2 } 2 (TMEDA)] (20) (30% thermal

ellipsoids).
[{Cd(L2)2}2(TMEDA)]
Cd(1)- N(3) 2.224(4) Cd(1)-N(6) 2.238(4)

Cd(1)-N(1) 2.356(4) Cd(1)-N(4) 2.369(4)
Cd(1)- N(7) 2.432(5) N(1)-C(9) 1.334(6)
N(1)-C(1) 1.364(6) N(2)-C(9) 1.364(6)

N(2)-C(10) 1.452(8) N(3)-C(9) 1.317(6)
N(3)-C(13) 1.461(7) N(4)-C(24) 1.334(6)
N(4)- C(16) 1.416(7) N(5)- C(24) 1.372(6)
N(5)-C(25) 1.453(7) N(6)-C(24) 1.318(6)
N(6)-C(28) 1.465(7)
N(3)-Cd(1 )-N(6) 145.4(1) N(3)-Cd(1 )-N(1) 58.3(1)
N(6)-Cd(1)-N(1) 110.6(1) N(3)-Cd(1)-N(4) 111.4(1)
80
N(6)-Cd(1 )-N(4) 58.5(1) N(1 )-Cd(1 )-N(4) 147.6(1)
N(3)- Cd(1 )-N(7) 111.3(2) N(6)-Cd(1)一 N(7) 103.4(1)
N(1)- Cd(1)—N(7) 109.9(1) N(4)-Cd(1)-N(7) 102.5(1)
C(9)一 N ⑴ 一 C(1) 122.4(4) C(9)-N(1)-Cd(1) 90.1(3)
C(1)-N(1)- Cd(1) 132.5(3) C(9)- N(2)-C(10) 126.5(5)
C(9)一 N(3) - C(13) 123.3(5) C(9)-N(3)-Cd(1) 96.5(3)
C(13)-N(3)-Cd(1) 140.2(4) C(24)-N(4)-C(16) 122.6(4)
C(24)-N(4)-Cd(1) 89.4(3) C(16)-N(4)-Cd(1) 133.8(3)
C(24)- N(5)- C(25) 124.9(4) C(24)-N(6)-C(28) 123.0(4)
C(24)-N(6)-Cd(1) 95.7(3) C(28)- N(6)- Cd(1) 141.1(3)
N(3)-C(9)-N(1) 114.8(4) N(3)-C(9)-N(2) 122.3(4)

N(1)-C(9)-N(2) 122.9(4) N(6)-C(24)-N(4) 116.3(4)
N(6)-C(24)-N(50 121.9(4) N(4)-C(24)-N(5) 121.8(4)
81
2.4 Summary for Chapter Two
A series of divalent metal [Mn(丨丨)，Fe(ll), Co(ll), Ni(ll), Zn(ll) and Cd(ll)]
complexes supported by the unsymmetrical guanidinate ligands
[(C6H3Me2-2，6)NC(NRR，)NR]- [R = CeHu, R，= H, (L1); R = C3H7, R ' = H (L2); R
=CeHu, R' = SiMes (L3)] were synthesized and characterized. The steric effect
of the guanidinate ligands L" (n = 1 - 3 ) on the structure of the corresonding
metal complexes were examined. Use of the sterically more bulky L 3 ligand
resulted in a decrease in coordination number of the metal center from five to
four: [{Mn(L 1 ) 2 } 2 (THF)] (7) and [{Mn(L 2 ) 2 }(TMEDA)] (8) versus [Mn(L 3 ) 2 ] (9). It
also forces the cobalt(ll) bis(guanidinate) complex [Co(L3)2] (14) to adopt a
square planar geometry, instead of the electronically more favorable
tetrahedral geometry.
Owing to the unsymmetrical nature of the L1，L2 and L 3 ligands, one
would expect the presence of conformational isomers in complexes 7，8, 14，
15 and 16. However, only one isomer for each of these complexes was
isolated and structurally characterized in our work. This may be ascribed to
different steric bulkiness of substituents attached to the nitrogen atoms on L 1 ,
L 2 and L 3 . However, the presence of other isomeric forms of these complexes,
such as cis-chelating isomers for square planar 14, 15 and 1 6 ， i n solution
could not be ruled out at this stage.
82
2.5 Experimental for Chapter Two
General Considerations
All manipulations were carried out under a purified nitrogen atmosphere using
modified Schlenk techniques.
Solvents were dried over and distilled from calcium hydride (hexane) or
sodium/potassium alloy (toluene) or sodium benzophenone (diethyl ether, THF,
pentane) and degassed twice by freeze-thaw cycles before use.
TMEDA (Alfa Aesar) was dried over and distilled from sodium before use. 2,6-
Dimethylaniline (IL) was dried over and distilled from potassium hydroxide.
A/,A/-Dicyclohexylcarbodiimide (Acros) was dissolved in hexane and dried over
anhydrous magnesium sulphate, and stored under nitrogen in a Schlenk flask.
Anhydrous Z n C b (Riedel de-Haen) was refluxed over SOCI2. N，N，-
Diisopropy丨carbodiimide (Aldrich), NiCI2 (Aldrich), CdCI2 (Aldrich), MnCI2
(Strem), FeCb (Strem) and C0CI2 (Strem) were used as received.
[2，6-Me2C6H3NH(SiMe3)] (3) and [Li{2，6-IV^2C6H3N(SiMe3)}(TMEDA)] (4) were
prepared according to procedures described previously.15
[Li(L 1 )(TMEDA)] (1): To a colorless mixture of 2,6-dimethylaniline (1.48 g, 12.0
mmol) and TMEDA (1.80 mL, 12.0 mmol) in diethyl ether (30 mL) was added
LiBu" (9.0 mL, 1.6 M, 14.0 mmol) at 0°C. The resulting solution was stirred at
room temperature for 4 hours. A colorless solution of N，N，-
dicyclohexylcarbodiimide (2.48 g, 12.0 mmol) in diethyl ether (10 mL) was
added to the above solution at 0°C. The reaction mixture was stirred at room
temperature for 8 hours and filtered. The filtrate was concentrated to afford
compound 1 as colorless crystals. Yield: 3.78 g, 70%. M.p.: 107 一 109。C. 1 H
83
NMR (400.13 MHz, C 6 D 6 ): 5 7.26 (d, J = 7.2 Hz, 2H， m-ArH), 6.89 (t, J = 7.2
Hz, 1H, p-ArH), 3.83 (d，J = 7.2 Hz, 1H，NH), 3.19，2.97 (m, 2H, NCeHu), 2.61
(s，6H, ArCH 3 ), 2.08 (m, 2H, NCeHu), 1.92 (s，12H, N(CH 3 ) 2 )，1.72 (s, 4H，
NCH 2 ), 1.52, 1.31, 1.09，0.92 (m，20H，NCeHu). 13 C NMR (100.61 MHz, C 6 D 6 ):
6 162.9 (CN 3 ), 153.9，129.8’ 128.2，117.4 (C 6 H 3 ), 56.4 (NCH2)，54.9, 51.9
(NCeHu) 45.5 (N(CH3)2)，38.0, 35.4’ 27.2，26.3, 25.9 (CeHu), 20.3 (ArCH 3 ).
Found: C, 72.36; H, 11.13; N, 15.59%. Anal. Calcd for C 27 H 48 UN 5 : C，72.12; H，
10.75; N，15.57%.
[Li(L 2 )(TMEDA)] (2): To a colorless solution of 2,6-dimethylaniline (2.12 g, 17.5
mmol) and TMEDA (2.6 mL, 17.5 mmol) in diethyl ether (30 mL) was added
LiBu n (11.0 mL, 1.6 M, 17.5 mmol) at 0°C. The resulting yellow suspension was
stirred at room temperature for 4 hours. A pale yellow mixture of N，N，-
diisopropylcarbodiimide (2.74 mL, 17.5 mmol) in diethyl ether (10 mL) was
added to the stirred suspension at 0°C. The resulting solution was stirred at
room temperature for 8 hours. The reaction mixture was filtered and the filtrate
was concentrated to afford compound 2 as colorless crystals. Yield: 4.87 g,
75%. M.p.: 79 一 80°C. 1 H NMR (300.13 MHz, C 6 D 6 ): 6 7.27 (d’ J = 7.2 Hz, 2H,
m-ArH), 6.90 (t，J = 7.2 Hz, 1H, p-ArH), 3.62 (br, 1H, NH), 3.52 (sept, J = 6.0
Hz 1H，NCH(CH 3 ) 2 ), 3.35 (sept, J = 6.0 Hz, 1H’ NC"(CH 3 ) 2 )，2.60 (s, 6H,
ArCHs), 1.89 (s, 12H，N(CH3)2, 1.70 (s, 4H, NCH 2 ), 1.24 (d, J = 6.0 Hz, 6H,
NCH(CH3)2)，0.92 (d，J = 6.0 Hz, 6H，NCH(CH3)2). 13 C NMR (75.47 MHz,
C6D6)： 6 162.8 (CN 3 ), 153.7, 129.6，129.0，116.9 (C 6 H 3 ), 56.4 (NCH2)，45.8
(N(CH 3 ) 2 ), 45.4，44.4 (NCH(CH3)2)，27.1，24.3 (NCH(CH3)2)，20.3 (ArCH 3 ).
84
Found: C, 68.88; H, 11.61; N, 19.28%. Anal. Calcd for C21H40UN5： C, 6 8 . 2 6 ; H，
10.91; N，18.95%.
[Li(L 3 )(TMEDA)] (5): To a colorless solution of compound 4 (5.93 g, 19.0
mmol) in diethyl ether (30 mL) was added A/,A/-dicyclohexylcarbodiimide (3.88
g, 19.0 mmol) at 0°C. The reaction mixture was stirred at room temperature for
8 hours. Concentration of the solution yielded complex 5 as colorless crystals.
Yield: 6.94 g, 70%. M.p.: 143 - 145°C. 1 H NMR (400.13 MHz, C6D6)： 6 7.20 (d,
J = 7.3 Hz, 2H， m-ArH), 6.93 (t, J = 7.1 Hz, 1H，p-ArH), 3.60 (br, 3H，NH,
NCeHu), 2.50 (s, 6H，ArCH3), 1.92 (s, 12H, N(CH 3 ) 2 ), 1.69 (s，4H, NCH 2 ), 1.30
(m，20H，NCeHu), 0.55 (s, 9H, Si(C" 3 ) 3 ). 13 C NMR (100.61 MHz, C6D6)： 5
152.8 (CN3)，137.9，131.5, 128.7，119.1 (C 6 H 3 ), 56.5 (NCH 2 ), 45.8 (N(CH3)2)，
38.8，36.8, 36.0，35.0, 27.0，26.6, 26.0，25.4 (C 6 Hn), 20.7 (ArCH 3 ), 5.6
(Si(CH3)3) Found: C, 69.73; H, 11.42; N, 13.61%. Anal. Calcd for CsoHseLiNsSi:
C, 69.05; H, 10.82; N, 13.42%.
[{Li(L 1 )(THF)} 2 ] (6): To a colorless mixture of 2,6-dimethylaniline (2.49 g, 21.0
mmol) in THF (30 mL) was added a solution of LiBu n in hexane (13 mL, 1.6 M,
21.0 mmol) at 0°C. A yellow suspension was obtained and stirred at room
temperature for 4 hours. A colorless solution of A/,A/-dicyclohexylcarbodiimide
(2.48 g, 12.0 mmol) in THF (10 mL) was added to the above suspension at
0°C. The resultant solution was stirred at room temperature for 8 hours and
concentrated to afford complex 6 as colorless crystals. Yield: 5.25 g，72%.
M.p.: 107 - 109°C. 1 H NMR (300.13 MHz, C 6 D 6 ): 6 7.14 (s，2H, m-ArH), 6.90
(t, J = 6.9Hz, 1H, p-ArH), 3.78 (d，J = 8.7Hz, 1H, NH), 3.52 (m, 4H, THF), 3.07,
85
2.89 (br, 2H, NCeHu), 2.44 (s, 6H，ArCH3), 1.98, 1.76, 1.62 (m, 14H，NCeHu),
1.36 (m, 4H, THF), 0.98, 0.81 (m，6H，NCeHu). 13 C NMR (75.47 MHz, C6D6)： 6
162.5 (CN 3 ), 151.2, 131.2，129.3，119.5 (C 6 H 3 ), 68.1 (THF), 56.0，52.0，37.4，
35.4，26.7, 26.5，26.0，25.7 (NC 6 H 22 ), 25.6 (THF), 19.8 (ArCH 3 ). Found: C，
73.73; H，10.50; N, 10.73%. Anal. Calcd for LiC 25 H 40 N 3 O: C，74.04; H，9.94; N，
10.36%.
General Procedure for the Synthesis of Compounds 7-14 and 17-20: To a
suspension of MCb in an appropriate solvent was added a colorless solution of
the lithium guanidinate complexes [Li(L n )(TMEDA)] in diethyl ether at 0°C. The
reaction mixture was stirred at room temperature for 8 hours. The resulting mixture
was filtered and the filtrate was concentrated to afford the desired product.
[Mn(L1)2(THF)] (7): MnCI2 (0.28 g，2.2 mmol). [Li(L 1 )(TMEDA)](1) (1.93 g, 4.3
mmol). Solvent: Toluene. The reaction mixture was filtered and the filtrate was
concentrated in vacuo. THF (0.5 mL) was added to afford complex 7 as pale
yellow crystals. Yield: 1.23 g, 56%. M.p.: 130 — 132 °C (dec). |j eff = 5.55 |JB.
Found: C，71.32; H, 9.28; N，11.33%. Anal. Calcd for C46H72MnN6〇：C, 70.83;
H, 9.30; N, 10.77%.
[{Mn(L 2 ) 2 } 2 (TMEDA)] (8): MnCI2 (0.44 g，3.5 mmol). [Li(L 2 )(TMEDA)] (2) (2.48
g, 6.7 mmol). Solvent: Diethyl ether. The reaction mixture was filtered and the
filtrate was concentrated to afford complex 8 as pale yellow crystals. Yield:
I.49 g, 40%. M.p.: 104 - 1 0 6 ° C . p eff = 4.24 [JB. Found: C, 64.80; H, 9.94; N,
16.48%. Anal. Calcd for C66H112Mn2N14: C, 65.43; H, 9.32; N，16.18%.
86
[Mn(L3)2] (9): MnCI 2 (0.30 g, 2.4 mmol). [Li(L 3 )(TMEDA)] (5) (2.50 g，4.9
mmol). Solvent: Diethyl ether. The reaction mixture was stirred at room
temperature for 8 hours. All the volatiles were removed in vacuo. Toluene was
used to extract the solid residue. The reaction mixture was filtered and the
filtrate was concentrated to afford compound 9 as pink crystals. Yield:1.21 g,
57%. M.p.: 113 - 115°C. |JEFF = 5.67 |JB. Found: C, 68.20; H，10.02; N, 9.68%.
Anal. Calcd for C 48 H 80 MnN 6 Si 2 : C, 67.64; H，9.46; N, 9.86%.
[Fe(L2)2] (10): FeCI2 (0.48 g, 3.8 mmol). [Li(L 2 )(TMEDA)] (2) (2.73 g，7.4
mmol). Solvent: Toluene. The reaction mixture was stirred at room temperature
for 8 hours. All the volatiles were removed in vacuo. Pentane was used to
extract the residue. It was filtered and the filtrate was concentrated to yield
compound 9 as pale yellow crystals. Yield: 1.93 g, 50%. M.p.: 198 一 200°C
(dec), peff = 4.98 [Jb. Satisfactory results of elemental analysis could not be
obtained for this compound.
[Fe(L3)2] (11): FeCI2 (0.30 g, 2.4 mmol). [Li(L 3 )(TMEDA)] (5) (2.48 g，4.8
mmol). Solvent: Diethyl ether. The reaction mixture was filtered to remove LiCI
and the filtrate was concentrated to yield compound 11 as green crystals.
Yield: 1.65 g, 81%. M.p.: 200 - 202°C (dec). |Jeff = 4.89 |JB. Found: C, 67.85; H，
9.83; N, 10.01. Anal. Calcd for C48H8oFeN6Si2： C, 67.57; H，9.45; N, 9.85.
[ C O ( L 1 ) 2 ] ( 1 2 ) : C0CI2 ( 0 . 4 0 g, 3 . 0 mmol). [Li(L 1 )(TMEDA)] (1) ( 2 . 7 2 g，6.0
mmol). Solvent: Diethyl ether. The reaction mixture was filtered and the filtrate
was concentrated to yield complex 12 as violet crystals. Yield: 1.47 g, 70%.
87
M.p.: 150 一 152。C. |Jeff = 5.38 Found: C, 70.63; H, 9.20; N, 12.12. Anal.
Calcd for C 4 2H 6 4N 6 Co: C，70.86; H, 9.06; N，11.80.
[CO(L 2 ) 2 ] (13): C0CI2 (0.35 g, 2.6 mmol). [Li(L 2 )(TMEDA)] (2) (2.94 g, 7.9
mmol). Solvent: Diethyl ether. The reaction mixture was filtered to remove LiCI
and the filtrate was concentrated to afford complex 13 as violet crystals. Yield:
3.12 g，80%. M.p.: 104 一 106°C. |j eff = 5.00 |JB. Found: C，65.32; H, 8.89; N，
15.67. Anal. Calcd for C3oH48N6Co: C, 65.31; H, 8.77; N, 15.23.
[CO(L 3 ) 2 ] (14): C0CI2 (0.35 g, 2.6 mmol). [Li(L 3 )(TMEDA)] (5) (2.69 g, 5.2
temperature for 8 hours. The solvent was removed in vacuo. The residue was
extracted with toluene (20 mL). The extract was concentrated to afford
compound 14 as brown crystals. Yield: 1.57 g, 70%. M.p.: 164 一 165°C. |jeff =
4.89 MB. Found: C，67.16; H, 9.58; N，10.09. Anal. Calcd for C48H8oN6CoSi2: C,
67.33; H，9.42; N，9.81.
[NI(L 1 ) 2 ] (15): To a light brown suspension of NiCI2 (0.34 g, 2.7 mmol) in THF
(20 mL) was added TMEDA (0.4 mL, 2.7 mmol). The reaction mixture was
heated at 60°C for 1 day, where upon the reaction mixture changed from light
brown to green-grey suspension. A colorless solution of [Li(L 1 )(TMEDA)] (1)
(2.36 g, 5.3 mmol) in THF was added at 0°C. The reaction mixture was stirred
at room temperature for 8 hours. The solvent was removed in vacuo. The
residue was extracted with diethyl ether (20 mL). The extract was concentrated
to yield compound 15 as deep blue crystals. Yield: 1.15 g，60%. M.p.: 202 -
88
205°C. 1 H NMR (300.13 MHz, C 6 D 6 ): 5 6.88 一 6.98 (m, 3H，C 6 H 3 )，3.15 (s, 6H,
ArCH 3 ), 2.89 (d，1H，NH)，2.59, 1.90 (m, 2H, NCeHu), 1.72, 1.50，1.30，0.98，
0.75, 0.46 (m, 20H, NCeHu). 13 C NMR (75.47 MHz, C 6 D 6 ): 6 163.1 (CN 3 ),
146.1，136.7，128.3’ 123.9 (C 6 H 3 ), 52.1，51.3, 34.9, 34.2, 34.0，26.3，25.5
(NCeHu), 20.1 (ArCH 3 ). Found: C，71.60; H, 9.42; N，12.23%. Anal. Calcd for
C 42 H 64 N 6 Ni: C，70.88; H, 9.06; N, 11.80%.
[Ni(L2)2] (16): Compound 16 was prepared by a procedure similar to that of
compound 15，starting with NiCI2 (0.29 g, 2.3 mmol), TMEDA (0.3 mL, 2.3
mmol) and [Li(L 2 )(TMEDA)] (2) (1.40 g, 3.8 mmol). The product mixture was
extracted with hexane, yielding 16 as deep blue crystals. Yield: 1.08 g，50%
M.p.: 160 - 162°C. 1 H NMR (300.13 MHz, C6D6)： 5 6.90 - 7.00 (m, 3H, C6H3),
3.11 (s，6H，ArCHs), 2.89 (sept, J = 6.3 Hz, 1H, NCH(CH3)2)，2.61 (d, J = 9.9
Hz, 1H，NH), 2.22 (sept, J = 6.3 Hz, 1H，NCH(CH3)2), 0.61 (d, J = 6.6 Hz, 6H，
NCH(CA73)2)，0.52 (d, J = 6.6 Hz, 6H，NCH(CH 3 ) 2 ). 13 C NMR (75.47 MHz,
C 6 D 6 ): 5 163.2 (CN 3 )，146.1，136.5，128.4，123.9 (C 6 H 3 ), 44.0, 43.3
(NCH(CH3)2)，23.9, 23.4 (NCH(CH3)2)，20.0 (ArCH 3 ). Found: C, 65.86; H，9.03;
N，15.78%. Anal. Calcd for C 30 H 48 N 6 Ni: C, 65.34; H, 8.77 N, 15.23%.
[Zn(L1)2] (17): ZnCI 2 (0.35 g，2.5 mmol), [Li(L 1 )(TMEDA)] (1) (2.18 g, 4.8
temperature for 8 hours. The reaction mixture was filtered and the filtrate was
concentrated to afford compound 17 as colorless crystals. Yield: 1.14 g, 45%.
M.p.: 1 5 7 - 159 °C. 1 H NMR (300.13 MHz, C 6 D 6 ): 6 7.06 (d, J = 7.2 Hz, 2H，m-
ArH), 6.94 (m, 1H, p-ArH), 3.75 (d, 1H, NH), 3.05’ 2.87 (m, 2H，NCeHu), 2.41
89
(s，6H，ArCH3), 2.00, 1.80，1.61，1.32, 0.78, 0.61 (m，20H，NCeHu). 13 C NMR
(75.47 MHz, C 6 D 6 ): 6 162.6 (CN 3 ), 146.6，133.4，128.4, 122.3 (C 6 H 3 ), 53.3,
51.8，36.6，34.8，34.2, 26.5，25.6, 25.4 (NCeHu), 19.3 (ArCHs). Found: C,
70.10; H, 9.46; N, 12.17%. Anal. Calcd for C42H64N6Zn: C, 70.22; H，8.98; N,
11.69%.
[Zn(L2)2] (18): ZnCI 2 (0.27 g, 2.0 mmol). [Li(L 2 )(TMEDA)] (2) (1.48 g，4.0
concentrated to yield compound 18 as colorless crystals. Yield: 0.51 g, 46%.
M.p.: 115 - 117°C. 1 H NMR (300.13 MHz, C6D6)： 5 7.04 (d，J = 7.5 Hz, 2H, m-
ArH), 6.90 (m，1H, p-ArH), 3.52 (d, 1H, NH), 3.14 一 3.23 (m, 2H, NCH(CH 3 ) 2 ),
2.36 (s，6H, ArCH3), 1.14 (d，J = 6.0 Hz, 6H, NCH(CH 3 ) 2 ), 0.64 (d，J = 6.3 Hz,
NCH(CH3)2). 13 C NMR (75.47 MHz, C6D6)： 5 162.6 (CN 3 ), 146.4，133.1, 128.4，
122.1 (C 6 H 3 ), 45.2，44.3 (NCH(CH3)2)，25.8，23.8 (NCH(CH3)2)，19.3 (ArCH 3 ).
Found: C, 64.18; H, 9.11; N, 15.56%. Anal. Calcd for C3oH48N6Zn: C, 64.56; H,
8.67; N, 15.05%.
[Zn(L3)2] (19): ZnCI 2 (043 g，3.2 mmol). [Li(L 3 )(TMEDA)] (5) (3.03 g, 5.8 mmol).
Solvent: Diethyl ether. The reaction mixture was stirred at room temperature for
8 hours. The reaction mixture was filtered and the filtrate was concentrated to
afford compound 19 as colorless crystals. Yield: 0.67 g, 24% M.p.: 182 一 183
。C (dec). 1 H NMR (300.13 MHz, C6D6)： 5 6.86 一 7.05 (m, 3H, C 6 H 3 ), 3.10 一
2.30 (m, 3H, CeHu), 2.13 一 2. 58 (m, 6H, ArCH 3 ), 1.95，1.61, 1.33, 1.12, 0.81
(m，19H, C e H u ) , 0 . 3 7 (s, 9 H ， S i ( C H 3 ) 3 ) 13C N M R ( 1 0 0 . 6 1 M H z , C 6 D 6 )： 5 170.8
90
(CN 3 ), 146.1，133.3, 132.8，122.6 (C6H3)，65.9，62.0，54.9，38.1, 37.0’ 36.1，
35.4, 27.8, 27.4，26.4，26.1, 20.1 (NC 6 Hn), 19.6，15.6 (ArCHs), 4.83 (Si(CH 3 ) 3 ).
Found: C, 66.85; H，9.32; N，9.61%. Anal. Calcd for C48H8oN6ZnSi2: C, 66.82
H，9.35; N, 9.74%.
[{Cd(L 2 ) 2 } 2 (TMEDA)] (20): CdCI 2 (0.35 g，1.9 mmol). [Li(L 2 )(TMEDA)] (2) (1.40
g, 3.8 mmol). Solvent: Diethyl ether. The reaction mixture was stirred at room
concentrated to afford compound 20 as colorless crystals. Yield: 0.54 g, 28%.
M.p.: 116 - 118°C. 1 H NMR (400.13 MHz, C 6 D 6 ): 6 7.08 (d, J = 7.4 Hz, 4H，m-
ArH), 6.91 (t, J = 7.4 Hz, 2H, p-ArH), 3.45 (br, 2H, NH), 3.21 一 3.28 (br, 4H,
NCH(CH3)2)，2.41 (s, 2H， NCH2 ), 2.40 (s, 12H，ArCH3), 2.14 (s, 6H, N(CH 3 ) 2 ),
1.07 (d，J = 5.1 Hz, 12H, NCH(CH 3 ) 2 ), 0.68 (d，J = 5.5 Hz, 12H，NCH(CH3)2).
13 C NMR (100.61 MHz, C6D6)： 5 147.5 (CN 3 ), 132.7，129.1，128.5, 121.8
(C 6 H 3 ), 58,3 (NCH2)，46.2 (N(CH3)2)，45.6, 44.7 (NCH(CH 3 ) 2 ), 26.2，23.9
(N(CH(CH3)2)，19.5 (ArCH 3 ). Found: C, 59.53; H, 9.02; N, 15.09%. Anal. Calcd
for C66Hii2Cd2Ni4： C，59.76 H, 8.51; N, 14.78%.
91
Chapter Three: Synthesis and Structural Characterization of
Mono(guanidinate) Complexes of Mn(ll)，Fe(ll)
and Cu(l)
3.1 Introduction
3.1.1 Introduction of Mono(guanidinate) Complexes of the First-Row
Divalent Transition Metals
Among all the first-row divalent late transition metal complexes
supported by guanidinates and amidinates, seven structural motifs are
generally observed in the literature.1"9 They are shown in Chart 3-1.
R'
R R 、 A | ^ R R R R
R R \ I \ / \ /
M
“X仏 f h —L—M《h
N �N / \ / \ / \
R/ \R R / T
N N 、 R R R R
r
R,
* ㈧（B) (c)
R x R R R
K 入
R\
J s -,x K》
R _ ~ < ( M : : u — ( I rR , ’、）、、M’、、J
r r
、，礼
x r
R / x R R
(D) R (E) (F) (G)
R' = N(R)2, CR, H
L = Bidentate donor ligand
S = Solvent
X = Halide
Chart 3-1
Representative examples of these structure motifs are provided in Table 3-1.
Among these seven structures, bis(guanidinate/amidinate) complexes (A-C)
are commonly observed.1-8 On the other hand, mono(guanidinate/amidinate)
complexes (D-G) of the first-row divalent transition metals are rare.3，8,9 They
have received less attention because of the difficulty in their preparations.

95
Regardless of synthetic pathways employed, the corresponding
bis(guanidinate) complexes tend to be the isolated products. To our
knowledge, only one example of mono(guanidinate) late transition metal
complex has been reported. 6 The iron(ll) mono(guanidinate) complex [FeBr{|j-
n 2 -(CyN) 2 C(HNCy)}] 2 was prepared by the reaction of [Li{n 2 -(CyN) 2 C(HNCy)}]
with an equimolar amount of FeB「2 (Scheme 3-1).
Br Cy
c y � « + - ^ ^ h
Li N ^ \
n / Br
Cy
Scheme 3-1
However, it is not always successful to prepare mono(amidinate/guanidinate)
metal complexes by simply employing a 1:1 stoichiometric ratio of the reagents
in metathesis reactions. Alternatively, Arnold et al. and coworkers also
synthesized the mono(amidinate) nickel(ll) complex [Ni{r| 2 -{2，6-(4-
BufPh)}2PhC(NPr02}(acac)] by reacting the lithium amidinate [Li{q 2 -{2,6-(4-
Bu f Ph)} 2 PhC(NPr')2}(TMEDA)] with an equimolar amount of nickel(ll)
bis(acetylacetonato) complex (Scheme 3-2). 9
會<;〕+« __.
Scheme 3-2
Mono(guanidinate/amidinate) metal complexes have been shown to
exhibit a wide range of reactivities, such as reduction 10 and substitution.11
Since mono(guanidinate/amidinate) complexes of divalent late transition
96
metals are not easy to synthesize, studies on their reactivity are scarce. The
reactivity of an iron(ll) mono(guanidinate/amidinate) complex was first reported
by Hessen and coworkers. 9 The binuclear Fe(ll) mono(amidinate) complex
[Fe(n2-{PhC(NC6H3Pr/2-2,6)2})CI(|j-CI)Li(THF)3] was reacted with Li(CH 2 SiMe 3 )
to give the corresponding alkyl derivative [Fe(n2-{PhC(NC6H3Pr2-2，6)2}
(CH 2 SiMe 3 )(py)] (Scheme 3-3).
Ar Ar SiMe3
丨(THF)3 圆 2 • 幻 � p h
V
pyridine
.'、飞，、 y
J /
Ar Ar
Ar = C6H3PIV2，6 -
Scheme 3-3
Table 3-1. Examples of the seven structural motifs.

Structural Motifs Examples
Bu f \ Bu' Ar Ar
M e
i>^Me Ph
• i>^Ph
N 、N / \ f / \
/ \ Bu( Buf Ar Ar
R R Ar= C6H3Me2-2，6
(A) M = Mn, Fe, Co, Ni M = Mn, Fe, Co, Ni
Lim et a 1.5 Hessen and coworkers.4
Cy、 N,,, I (、、、N Cy

N~ ( ( ' Fe Fe ' U~ N
H ^ ^ \ / V H
cy cy
r
R
、人 R … 广 T、、
V I \ J < 、
/, \ / \ Z \\ Richeson et al.6
R \ I \
R / N ^ ^ N 、 R H
R I Cy I c Cy
r, \ ii \ y
(B) MN.
广 d N\
c / c y 丫 cy cy
H
Sandro and Thompson7
97
~ - — —^“丨…丨丨丨丨丨丨…丨丨丨丨川I丨…丨丨丨 1 1 1 1 1 1 1 1 1 1 1 丨丨丨 1 丨丨丨丨丨丨
Structural Motifs Examples

—
Ar Ar
R R Ph / A\ Ph
\ / WN N^/
Me 3 Si — N / , . I \NCi...、N—SiMe3
N、、、 ’"N
/ \ Ph \ / Ph
R R Ar Ar
(C) Ar = C6H3Me2-2,6
Lee et a/.8
R、 \
N X N ci
R'-/(VM：''、、：Li — ( S ) n
P h ~(( X U ( T H F ) 3
V、、、X, N '"CI
R/ A/
^ ‘ Hessen et a/.9
x R Br 产
R / N Cy\/ /、 H
R7 X c/ Br
(E) Richeson et al.6
Ar
.
R\
N.
X
//V / /
V 尸f
//V ‘ Ph~(( Fe—N^"
R'—{( .M、、 1、、、. \ \
K、、j r V
/ Me3Si
R
K
(f) Ar = C6H3Me2-2，6
8
^ ‘ Lee et a/.
R7 - ¾ ^
(G) \
Arnold et a 1. 3
98
3.1.2 Alkyl Complexes of the Late Transition Metals
Alkyl complexes of late transition metals have attracted much research
interest because of their potential applications in the catalytic olefin
polymerization. 12 ' 13 ’ 24 The alkyl complexes are used as catalyst precursors.
They are to be activated by alkyl abstraction reagents. The resulting cationic
species with an active M - C bond will participate into the polymerization
reaction.
Alkyl complexes of transition metals are very unstable. As a result, they
are often stabilized by the neutral or anionic ancillary ligands. Charts 3-2 and
3-3 illustrate some examples of bidentate and tridentate ancillary ligands.
Ar-N N-Ar Ar^ Âr N ㊀

N
Ar = C e H a P ^ . G Ar = C6H3Pr'2-2,6 Ar = C6H3Pr'2-2，6
Bart et a/.14 R = Me, Buf Hessen et a/.9
Holland et a/.15-16
Roesky et al.u
‘ Chart 3-2
N-N
H
-級：• I \\ N N
P r ' ^ V ^ P r ' A / \ r
Akita et al. 18—21 Gibson et al.22
Chart 3-3
A number of monoalkyl complexes with stabilizing ligands have been reported,
9,18-21 however, they were shown to be inactive or to have a low reactivity
towards polymerization reactions. Considerable efforts have been devoted into
the modification of stabilizing ligands. The monoalkyl iron(ll) complex 99[{r|2-
PhC(NC6H2Me3-2，4，6)2}Fe(CH2SiMe3)(p力]has been shown to be active

towards olefin polymerization after being activated by either aluminoxanes or
tris(pentafluorphenyl)borane. 24 Complexes supported by a neutral pyridine-2，6-
diimine (PDI) ligand (Chart 3-4) have also been shown to be highly active
towards olefin polymerization. 12 - 13
n
/N N\
Ar = C6H3Pr'2-2,6
PDI ligand
Chart 3-4
100
3.1.3 Introduction of Mono(guanidinate) Complexes of Cu(l)
Group 11 metal complexes supported by amidinato ligands have found
to be useful in material science，such as CVD and ALD applications. 26 The first
Group 11 metal guanidinate complexes [Cu2{[>n 2 -(Pr'N) 2 CR}2] (R = NMe2,
N(H)Pr') were synthesized by the metathesis reaction of copper(l) chloride and
the corresponding lithium guanidinates [Li{n 2 -(Pr'N) 2 CR}] (R = NMe2, N(H)Pr')
(Scheme 3-4). 27 Group 11 metals tend to form dinuclear complexes with
bridging guanidinate ligands. Tetrameric and hexameric copper(l) guanidinate
clusters have also been reported. 28 These oligonuclear copper compounds
usually contain a short Cu …Cu interatomic distance which plays an important
role in biological systems. 29
R
Pr' 卞
R
Pr' JL pr'
+ 2CuCI : • Cu Cu
\ hexane, r. t., 18h
R = NMe2，N(H)Pr' p r' Pr'
R
Scheme 3-4
101
3.2 Objectives of Our Study
Guanidinate ligands have been widely employed in stabilizing transition
metal complexes. 1 , 2 However, reports on mono(guanidinate) complexes have
been rare. In fact, bis(guanidinate) complexes were always the prepared
products, despite the stoichiometric ratio of reagents used. The scarcity of
mono(guanidinate) complexes of the first-row divalent late transition metals
has attracted our attention.
In this research work, mono(guanidinate) complexes of the type [M(L 3 )
(TMEDA)(CI)] (L3 = [(C6H3Me2-2，6)NC(N(Cy)(SiMe3))N(Cy)]-; M = Mn 21，Fe
22) were synthesized. A preliminary study on the reactivity of complexes 21
and 22 towards LiMe was also examined. A copper(l) mono(guanidinate)
complex (24) supported by the L 2 ligand ([(C6H3Me2-2，6)NC(N(Pr')(H))N(Pr')]-)
was prepared.
102
3.3 Results and Discussion
3.3.1 Synthesis and Structures of Mono(guanidinate) Complexes
Supported by L 3
3.3.1.1 Synthesis of [M(L 3 )(TMEDA)(CI)] (M = Mn 21，Fe 22) Complexes
Supported by L 3
Mono(guanidinate) complexes of the type [M(L3)(TMEDA)(CI)] (M = Mn
21，Fe 22) were synthesized by the reaction of anhydrous MCb with one molar
equivalent of [Li(L 3 )(TMEDA)] (5) in diethyl ether. (Scheme 3-5)
Cy^ ^SiMe3 SiMe3

f Y I Cy-N 产
c y
人 , ™
\ o U \ / Et 2 0, r. t., 8h ZM\—CI
/N N、 \ 二 \ ,
(5) M = Mn 21 (47%)
. M = Fe 22 (37%)
Scheme 3-5
Compounds 21 and 22 were isolated as pale yellow crystals in 47%
and 37% yield (based on the ligand used), respectively. The appearance of the
mono(guanidinate) complexes are in great contrast to the corresponding
bis(guanidinate) complexes.
The solid-state structures of compounds 21 and 22 were determined by
X-ray diffraction studies. Results of elemental analysis were consistent with
the empirical formula of the two complexes. Solution magnetic moments of 21
(5.61 |j B ) and 22 (5.07 \jq) were determined by the Evans NMR method. They
103
are consistent with the spin-only value of 5.92 |JB and 4.90 |JB for a high-spin
d 5 and d 6 electronic configuration, respectively. Some physical properties of
compounds 21 and 22 are shown in Table 3-2.

Moment (MB) Crystals
‘ " , “.....7 , � ‘ ^ W m ^ M f ^ ^ ^ ^ ^ M ^ K w w A
21 47 5.61 Pale Yellow 214-216
22 37 5.07 Pale Yellow 104-106 (dec)
3.3.1.3 Molecular Structures of Compounds 21 and 22
X-Ray quality crystals of compounds 21 and 22 were grown from
toluene. Molecular structures of compounds 21 and 22 with the atom
numbering scheme are illustrated in Figures 3-1 and 3-2，respectively.
Selected bond distances and bond angles are provided in Tables 3-3 and 3-4.
Compounds 21 and 22 are mononuclear. Both compounds crystallize in
the monoclinic crystal system with the space group P2、lc. They are
isostructural with a distorted trigonal bipyramidal geometry. The central metal is
coordinated by two nitrogen atoms from a guanidinate ligand, two nitrogen
atoms from a TMEDA ligand molecule, and one terminal chlorine atom. The
axial positions are occupied by N(3) and N(5). It is believed that the N(3) atom,
which bears a cyclohexyl group, is situated at an apical position in order to
minimize steric repulsion. The M-N(3) and M-N(5) distances are longer than
the equatorial M-N(1) and M-N(4) bonds. The N(3)-M(1)-N(5) angles range
from 152.1(1) to 157.1(1)°. The equatorial plane is formed by N(1), N(4) and
Cl(1) with the sum of bond angles around the metal center being 360 0 .
104
The N(1)-M(1)-N(3) bite angles in 21 and 22 are 62.0(1)。and 62.2(1)°,
respectively. The M - N g — bond distances of 2.112(4) A and 2.212(4) A in
21 are comparable to those of 2.092(3) A and 2.161(3) A in 22.
The molecular structure of compound 22 is different from that of the
iron(ll) mono(guanidinate) complex [FeBr{|j-r|2-(CyN)2C(HNCy)}]2.6 The latter
complex has a binuclear structure. The Fe-NgUanidmate distances in 22 are
slightly shorter than those of 2.0363(18) A and 2.2557(17) A in [FeBr{|j-n 2 -
(CyN)2C(HNCy)}]2，6 and 2.083(2) A and 2.260(2) A in the Fe(ll) amidinate
complex [Fe{n 2 -PhC(SiMe3)(NC 6 H 3 Me 2 -2，6)}(TMEDA)(CI)]. 8
105
o017
ci3 l r
C29 0 2 8
Figure 3-1 • Molecular structure of [Mn(L 3 )(TMEDA)(CI)] (21) (30% thermal

ellipsoids).
1 1
[Mn(L3)(TMEDA){CIJ
Mn(1)-N(1) 2.112(4) Mn ⑴ - N ( 3 ) 2.212(4)
Mn(-1)-N(4) 2.290(4) Mn(1)-CI(1) 2.351(2)
Mn(1)-N(5) 2.359(4) Si(1)-N(2) 1.747(4)

N(1)- C(9) 1.342(5) N(1)- C(1) 1.410(5)
N(2)-C(9) 1.415(5) N(2)-C(10) 1.505(6)
N(3)-C(9) 1.321(5) N(3)- C(19) 1.456(5)
N(1)-Mn(1)-N(3) 62.0(1) N(1)—Mn ⑴ 一 N(4) 129.9(1)
N(3)-Mn(1)-N(4) 100.5(1) N(1)-Mn(1)-CI(1) 125.0(1)
N(3)-Mn(1 )-CI(1) 111.0(1) N(4)-Mn(1 )-CI(1) 105.0(1)
N(1 )-Mn(1) 一 N(5) 97.7(1) N(3)-Mn(1 )-N(5) 152.1 (1)
N(4)-Mn(1 )-N(5) 77.3(1) Cl(1 )-Mn(1)- N(5) 96.3(1)

C(9)-N(1 )-C(1) 123.8(3) C(9)-N(1 )-Mn(1) 94.0(3)
C(1 )-N(1 )-Mn(1) 141.3(3) C(9)-N(2)- C(10) 113.0(3)
106
C(9)一 N(2)-Si(1) 124.2(3) C(10)-N(2)-Si(1) 122.8(3)
C(9)"N ⑶ 一 C(19) 122.5(3) C(9)-N(3)-Mn(1) 90.2(2)
C(19)-N(3)-Mn(1) 138.0(3) N(3)-C(9)-N(1) 113.6(4)
N(3)-C(9)-N(2) 124.4(4) N(1) 一 C(9)-N(2) 122.0(4)
107
C22
C4
Figure 3-2. Molecular structure of [Fe(L3)(TMEDA)(CI)] (22) (30% thermal

ellipsoids).
[Fe(L3)(TMEDA)(CI)]
Fe(*1)-N(1) 2.092(3) Fe(1)-N(3) 2.161(3)

Fe(1)- N(4) 2.239(4) Fe(1)-CI(1) 2.287(1)
Fe(1)-N(5) 2.309(4) Si(1)-N(2) 1.746(3)
N(1 )-C(9) 1.337(5) N(1 )-C(1) 1.415(5)
N(2) - C(9) 1.436(5) N(2)- C(10) 1.500(5)

N(3)-C(9) 1.310(4) N(3)-C(19) 1.461(5)
N(1 hFe(1)—N(3) 62.2(1) N(1 )-Fe(1)一 N(4) 123.8(1)
N(3)-Fe(1)-N(4) 98.7(1) N(1)-Fe(1)-CI(1) 129.2(1)
N(3) - Fe(1)- Cl(1) 107.25(9) N(4)-Fe(1 )-CI(1) 106.6(1)
N(1 )-Fe(1)一 N(5) 100.2(1) N(3) - Fe(1 )-N(5) 157.1(1)
C(9)-N(1 )-C(1) 126.8(3) C(9)-N(1 )-Fe(1) 94.0(2)
C(1 )-N(1 )-Fe(1) 138.9(3) C ⑶-N(2)-C(10) 114.3(3)
108
C(9)-N(2)-Si(1) 122.9(3) C(10>"N(2)- Si(1) 122.8(3)
C(9)-N(3)-C(19) 122.0(3) C(9)-N(3)-Fe(10) 91.7(2)
C(19)-N(3)-Fe(1) 136.8(2) N(3)-C(9) - N(1) 112.2(3)
N(3)-C(9)-N(2) 124.1(4) N(1)-C(9)-N(2) 123.8(3)
109
3.3.2 Synthesis and Structure of Monoalkyl Metal (M = Mn, Fe) Complexes
Supported by the Guanidinate Ligand L 3
3.3.2.1 Synthesis of Monoalkyl Metal (M = Mn, Fe) Complexes Supported
by the Guanidinate Ligand L 3
SiMe3
C y 一 N 广
M = Mn / ^^N
1 equiv MeLi /
SiMe3 / “ ——Me
一/
cy 广-一乂、0<
f k J C ] 」 2 3 ( 5 1 % )
M一CI 乂
\ \NZ \ z \ JTS Cy 驗 3
\ /NC \ Cy -AJ N
^ \ / =^ , . Me3S丨-\N J C y + 人 Cy
\ 1 equiv MeLi \ /, \ 、
、、、
、\ “ I \ /
M = Mn 21,Fe22 、 /N + Li
Toluene, r. t .,8h Cy N, 、N 、〜
XCy …
^ 11 5
(48%)
Scheme 3-6
Treatment of compound 21 with one molar equivalent of LiMe in toluene at
room temperature gave the Mn(ll) guanidinate-methyl complex 23 as pale
yellow crystals in 51% yield (Scheme 3-6). Compound 23 is highly soluble in
toluene, hexane and pentane. Attempts to prepare the analogous Fe(ll)
guanidinate-methyl complex by the reaction of the Fe(ll) monoguanidinate
complex 22 with LiMe under a similar reaction were unsuccessful. Ligand
redistribution was observed, yielding a mixture of the iron(ll) bis(guanidinate)
complex [Fe(L3)2] (11) and a small amount of the lithium guanidinate [Li(L3)
(TMEDA)] (5) in 48% yield (based on the compound 11). A similar ligand
redistribution reaction upon alkylation of mono(guanidinate/amidinate)
complexes were reported in the literature.9 The reaction of the iron(ll)
mono(amidinate) complex [Fe(r|2-{PhC(NC6H3Pr'2-2，6)2})CI(|j-CI)Li(THF)3] with
110
LiCH(SiMe3)2 resulted in the formation of the iron(ll) bis(amidinate) complex
[Fe(n2-{PhC(NC6H3Pr/2-2J6)2})2].9 Nelkenbaum et a/, have also reported a
similar result upon alkylation of the nickel(ll) mono(amidinate) complex [Ni(n2-
{PhC(NSiMe3)2)(acac)] with MeLi-LiBr. 23 . The nickel(ll) bis(amidinate) complex
[Ni(r|2-{PhC(NSiMe3)2}2] was isolated after the reaction. Methylation of the
titanium(lll) mono(amidinate) complex [{r|2-PhC(NSiMe3)2}(|J-CI)TiCl2]2 has led
to the formation of ligand redistribution products [{r|2-PhC(NSiMe3)2}2Ti(CH3)2]2
and TiMe4.25
3.3.2.2 Physical Characterization of Compound 23
Compound 23 was characterized by X-ray crystallography, magnetic
moment measurement, melting-point determination and elemental analysis.
Results of elemental analysis were consistent with the empirical formula of
compound 23. The measured solution magnetic moment of 23 was in
agreement with the spin-only value 5.92 |JB for a high-spin d5 electronic
configuration. Some physical properties are depicted in Table 3-5.
Table 3-5. Physical properties of compound 23

Moment (|JB) Crystals
23 51 5.76 Pale brown 148-150
3.3.2.3 Molecular structure of Compound 23
X-Ray quality crystals of complex 23 were grown from pentane. The
molecular structure of compound 23 with the atom numbering scheme is
111
illustrated in Figure 3-3. Selected bond distances and bond angles are
presented in Tables 3-6.
Compound 23 is mononuclear and crystallizes in the triclinic crystal
system with the space group P2i/c. The manganese center is coordinated by a
methyl group, a chelating guanidinate ligand and a chelating TMEDA ligand,
resulting in a distorted trigonal bipyramidal coordination around the
manganese atom. The coordination sphere of compound 23 is similar to that of
compound 21. Two nitrogen atoms N(3) and N(4) occupy the axial positions
with the N(3)-Mn(1)-N(4) angle of 142.75(8)°. A more severe distortion from
linearity in the N(3)—Mn(1)-N(4) angle was observed in 23，as compared to
that of 152.1(1)。in compound 21. The equatorial plane is formed by N(1)，N(5)
and C(25) with the sum of bond angles around the manganese center being
360°. The N(1)-Mn(1)-N(3) bite angle is 60.71(7)°. The Mn-N gU anidinate bond
distances fall within the range of 2.170(2) 一 2.210(2) A, which are comparable
to the corresponding distances in 21.
The Mn-Cmethyi bond length of 2.148(3) A in 23 is shorter than the average
Mn-Cmethyi bond length of 2.273 A reported for the dimeric manganese(ll)
diketiminate-alkyl complex [Mn{|j-HC(CMeNAr) 2 }(|j-Me)] 2 (Ar = 2，6-Pr'2C6H3)，17
but falls within the range of 2.060(11) 一 2.249(4) A for Mn-C t e rminai methyl bond
length.17
112
C23
Figure 3-3. Molecular structure of [Mn(L 3 )(TMEDA)(Me)] (23) (30% thermal

ellipsoids).
[Mn(L 3 )(TMEDA)(Me)]
Mn(1) - C(25) 2.148(3) Mn(1)-N(1) 2.190(2)
Mn(1 )-N(3) 2.210(2) Mn(1 )-N(5) 2.394(2)
Mn(1 )-N(4) 2.410(2) Si(1 )-N(2) 1.759(2)
N(1 )-C(1) 1 -414(3) N(1 )-C(9) 1,333(3)
N(2)-C(10) 1.487(3) N(2)-C(9) 1.428(3)
N(3)-C(19) 1.465(3)
C(25)-Mn(1) 一 N(1) 125.2(1) C(25) - Mn(1 )-N(3) 116.4(1)
N(1) 一 Mn(1 )-N(3) 60.71 (7) C(25) - Mn(1 )-N(5) 109.0(1)
N(1 )-Mn(1 )-N(5) 125.80(8) N(3)-Mn(1) - N(5) 97.97(8)
C(25) - Mn(1 )-N(4) 100.3(1) N(1 )-Mn(1) 一 N(4) 93.61 (8)
N(3) - Mn(1 )-N(4) 142.75(8) N(5)-Mn(1 )-N(4) 74.57(8)
C(9)-N(1 )-C(1) 127.1(2) C(9)-N(1 )-Mn(1) 93.4(1)
C(1) 一 N(1 )-Mn(1) 139.4(1) C(9)-N(2)-C(10) 115.6(1)
113
C(9)-N ⑵ - S i ( 1 ) 121.1(1) C(10)-N(2)-Si(1) 123.1(1)
C(9)-N(3)-C(19) 119.8(1) C(9)-N(3)-Mn(1) 92.6(1)
C(19)-N(3)-Mn(1) 134.8(1) N(3)-C(9)-N(1) 113.2(2)
N(3) - C(9)-N(2) 123.1(2) N(1)-C(9)-N(2) 123.7(2)
114
3.3.3 Synthesis and Structure of a Copper⑴ Guanidinate Complex
Supported by L 2
3.3.3.1 Synthesis of a Copper(l) Guanidinate Complex Supported by L 2
The synthetic pathway for copper(l) guanidinate compound 24 is
illustrated in Scheme 3-7. Compound 24 was prepared by reacting Cul with an
equimolar amount of the potassium salt of the L 2 ligand in THF. The latter was
prepared in situ by reacting the potassium salt of 2,6-dimethylaniline with N，N，-
diisopropylcarbodiimide. The latter potassium salt was prepared in situ by
treatment of 2,6-dimethylaniline with KH in THF.
Pr'、 Pr'
u \ / w
f Y \ - / ( ) W
1 2 K H
’THF，rt.,4h ^
2 ^y^NH 2.2Pr'NCNPr') THF, r.t., 8h / V J! \
I 3.2Cul,THF, r.t. 8h P— Cu—N Pr /
24 (34%)
Scheme 3-7
Dimeric compound 24 was isolated as colorless crystals from diethyl
ether in 34% yield (based on the metal salt used). Compound 24 is relatively
stable. Its solution was changed from the colorless solution to blue green
solution slowly after exposure to air for several minutes.
3.3.3.2 Physical Characterization of Compound 24
Compound 24 was characterized by X-ray crystallography, 1 H and 13C
NMR spectrum, melting-point determination and elemental analysis. The 1 H
NMR spectrum of the compound showed two sets of resonance signals. This
may be attributed to the presence of two different conformers of the complex in
115
the solution state. Some physical properties of complex 24 are depicted in
Table 3-7.
Table 3-7. Physical properties of compound 24.

Compound Yield (%) Appearance of Crystals M.p; (°G)
24 34 Colorless 202-204
2.3.3.3 Molecular Structure of Compound 24
Good quality crystals of compound 24 were obtained from diethyl ether.
The molecular structure of compound 24 with the atom numbering scheme is
illustrated in Figure 3-4. Selected bond distances and bond angles are shown
in Table 3-8.
The binuclear complex 24 crystallizes in the monoclinic crystal system with
the space group C2/c. Each copper atom is coordinated by two guanidinate
ligands in a bridging fashion. The Cu-N bond distances cover the range of
1.880(2) - 1.882(1) A, which are comparable to those of [Cu2{Me2NC(NPr/)2}2]
(1.875(2) - 1.876(2) A) and [Cu2{Pr/(H)NC(NPr/)2}2] (1.871(2) - 1.875(2) A), 29
and the amidinate analogue [Cu 2 {MeC(NBu") 2 } 2 ] (1.877(2) A). 28 The Cu.…Cu
distance of 24 was 2.4249(8) A. It is close to the Cu-Cu distance (2.40 A) in
metallic copper and the Cu.…Cu distance (2.38 - 3.20 A) in dimeric copper(l)
compounds. 30 Only the trans-chelating isomer of complex 24 was isolated and
structurally characterized in this work. This may be attributed to the different
steric bulkiness of the N-substituents (2，6-Me2C6H3 and Pr') on the L 2 ligand.
The geometry of Cu(1 )-N(1 )-C(9)-N(3)'-Cu(2) is slightly twisted. This is
different from the structures reported for the Cu(l) amidinate complexes,
[Cu2{MeC(NPr')2}2] and [Cu2{MeC(NBun)2}2], which showed a planar C u - N - C -
116
N-Cu moiety.29 A twisted [Cu-N-C-N] 2 core of compound 24 is shown in Chart
3-5. The twisted ligand-copper plane is commonly observed in guanidinate
complexes.29-31-32 It is reported that the lone pair electrons of the uncoordinated
nitrogen atom participated in the 兀 - s y s t e m of N - C - N functionality, leading to
the pyramidalization of the coordinated nitrogen atoms.31-32
1 名 J
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Chart 3-5
117
^ Q Qcai
i
Figure 3-4. Molecular structure of [Cu 2 (L 2 ) 2 ] (24) (30% thermal ellipsoids).
…， [CU3(L2)2]
Cu(1)-N(1) 1.882(1) Cu(1)—N(1)’ 1.882(1)

Cu(1)- Cu(2) 2.4249(8) Cu(2)- N(3) 1.880(2)
Cu(2)-N(3)' 1.880(2) N(1 )-C(9) 1.346(3)
N(1 )-C(1) 1.421(3) N(2)-C(9) 1.370(3)
N(2) - C(10) 1.463(3) N(3)，一 C(9) 1.329(3)
N(3)-C(13) 1.473(3)
N(1 )-Cu(1 )-N(1 )， 172.9(1) N(3)'-Cu(1 )-N(3) 173.7(1)

C(9)-N(1 )-C(1) 121.1(1) C(9)-N(1 )-Cu(1) 119.8(1)
C(1)一N(1) 一 C u ( 1 ) 116.7(1) C(9)一N(2)_C(10) 126.7(2)

C(9)，一 N(3) - C(13) 120.7(2) C(9)'-N(3)-Cu(2) 119.3(1)
C(13)-N(3)-Cu(2) 120.0(1) N(3)，-C(9)-N(1) 119.6(2)

N(3)-C(9)-N(2) 120.3(4) N ( 1 ) - C ( 9 ) 一N ( 2 ) 120.1(2)
118
3.4 Summary for Chapter Three
Manganese(ll) and iron(ll) mono(guanidinate) complexes [Mn(L 3 )
(TMEDA)] (M = Mn 21，Fe 22) were synthesized and structurally characterized.
Their reaction with LiMe was also examined. The reaction of 21 with LiMe
afforded the corresponding guanidinate—methyl complex [Mn(L 3 )(TMEDA)]
(23). On the other hand, treatment of 22 with LiMe led the ligand distribution,
yielding [Fe(L 3 ) 2 ] (11) and [Li(L 3 )(TMEDA)] (5). The dimeric copper(l)
guanidinate complex 24 [Cu2(L 2 )2] was synthesized and characterized. The
Cu •…Cu distance was 2.4249(8) A.
3.5 Experimental for Chapter Three
[Mn(L3)(TMEDA)(CI)] (21): To a pale yellow suspension of MnCI2 (0.37 g，2.94
mmol) in diethyl ether was added a colorless solution of [Li(L 3 )(TMEDA)] (5)
(1.30 g, 2.50 mmol) in the same solvent (20 mL) at 0°C. The reaction mixture
was stirred at room temperature for 8 hours. All the volatiles were removed in
vacuo. The residue was extracted with toluene. The solution was filtered and
concentrated to give complex 21 as pale yellow crystals. Yield: 0.71 g, 47%.
M.p.: 214 一 216°C. |Jeff = 5.61 Found: C, 59.31; H，9.29; N, 12.06. Anal.
Calcd for CaoHseNsCIMnSi: C，59.53; H, 9.32; N，11.56.
[Fe(L 3 )(TMEDA)(CI)] (22): To a pale yellow suspension of FeCI2 (0.50 g, 3.97
mmol) in diethyl ether was added a colorless solution of [Li(L 3 )(TMEDA)] (5)
(1.99 g, 3.82 mmol) in the same solvent (20 mL) at 0°C. The reaction mixture
was stirred at room temperature for 8 hours. All the volatiles were removed in
vacuo. The residue was extracted with toluene. The solution was filtered and
119
concentrated to afford complex 22 as pale yellow crystals. Yield: 0.85 g，37%.
M.p.： 104 - 106。C (dec). |jeff = 5.07 UB. Found: C, 59.47; H，9.43; N, 12.22.
Anal. Calcd for CaoHseNsCIFeSi: C, 59.44; H，9.31; N, 11.55.
[Mn(L 3 )(TMEDA)(Me)] (23): To a pale yellow solution of compound 21 (1.12 g,
1.85 mmol ) in toluene was added a pale yellow solution of MeLi (1.1 mL, 1.6M
in diethyl ether, 1.90 mmol) at -5°C. The reaction mixture was stirred at room
temperature for 8 hours. All the volatiles were removed in vacuo. The residue
was extracted with pentane. The solution was filtered and concentrated to yield
complex 23 as pale brown crystals. Yield: 0.55 g, 51%. M.p.: 148 - 150°C. |Jeff
= 5 . 7 6 MB. Found: C, 63.80; H, 10.67; N, 12.24. Anal. Calcd for CsiHsgNsMnSi:
C，63.66; H，10.17; N, 11.97.
[CU2(L2)2] (24): To a grey suspension of KH (0.10 g，2.50 mmol) in THF (20
mL) was added a colorless solution of 2,6-dimethylaniline (0.28 g, 2.30 mmol)
at 0 o C. The reaction mixture was stirred at room temperature for 4 hours and
filtered. A colorless solution of A/,A/-diisopropylcarbodiimide (0.36 mL, 2.30
mmol) was added to the filtrate at 0。C. The resultant solution was stirred at
room temperature for 8 hours, and added to a slurry of Cul (0.40 g, 2.20 mmol)
in THF (20 mL) at 0 o C. A pale yellow suspension was observed and stirring
was continued at room temperature for 8 hours. All the volatiles were removed
in vacuo. Diethyl ether was added and filtered. The filtrate was concentrated to
yield colorless crystals of compound 24. Yield: 0.23 g, 34%. M.p.: 202 - 204。C.
1H NMR (400.13MHz, C 6 D 6 ): 6 7.08 (d，J =7.6 Hz, 2H, m-ArH), 7.01 (d，J = 7 . 3
Hz, 2 H ， m-ArH), 6.91 (m, 2H，p-ArH), 3.38 (sept, J = 6 . 4 Hz, 1H，NCH(CH3)2)，
120
3.32 (m, 2H，NH), 3.17 (m，1H，NCH(CH3)2)，3.14 (sept, J = 6.3 Hz, 1H,
NC"(CH 3 )2)，3.03 (sept, J = 6.4 Hz, 1H, NCH(CH 3 ) 2 ), 2.59 (s, 6H，ArCH3), 2.39
(s，6H，ArCH3), 2.14 (s, 6H，N(CH3 )2 )，1.32 (d，J = 6.2 Hz, 6H, NCH(CH 3 ) 2 ),
1.06 (6, J = 6.2 Hz, 6H, NCH(CH 3 ) 2 )’ 0.65 (d, J = 6.2 Hz, 6H，NCH(CH3)2), 0.57
(d，J = 6.4 Hz, 6H，NCH(C"3)2). 13 C NMR (100.61 MHz, C6D6)： 6 165.9，165.8
(CN 3 ), 148.3，148.0，133.4，132.8，128.9，123.0，122.4 (ArCJ，48.1，48.0, 46.0，
45.7 (NCH(CH3)2)，27.1，27.0, 24.0 (N(CH(CH 3 ) 2 ), 19.8 (ArCHs). Found: C,
57.43; H, 8.20; N, 13.90. Anal. Calcd for C3oH48Cu2N6: C, 58.13; H，7.81; N，
13.55.
121
3.6 References for Chapter Three
1. Bailey, P. J.; Pace, S. Coord. Chem. Rev. 2001, 214, 91-141.
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6. Foley, S. R.; Yap, G. P. A.; Richeson, D. S. Inorg. Chem. 2002，16, 4149一
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10.(a) Green, S. P.; Jones, C.; Junk, P. C.; Lippert, K. -A.; Stasch, A. Chem.
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11.(a) Duchateau, R.; Meetsma, A.; Teuben, J. H. Organometaliics 1996，15,
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14. Bart, S. C.; Hawrelak, E. J.; Schmisseur, A. K.; Lobkovsky, E•； Chirik, P. J.
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124
Appendix 1
Physical Measurements
1H and 13 C NMR spectra were recorded on a Bruker DPX 300 NMR
spectrometer at 300.13 MHz and 75.47 MHz, and Bruker Advance III 400
NMR spectrometer at 400.13 MHz and 100.13 MHz. All of the spectra were
measured in ofe-benzene (〇6D6) and the chemical shifts 5 were referenced to
the residual peaks of solvent protons at 7.16 ppm in 1 H NMR, and 128.06 ppm
in 13 C NMR. Melting-point determinations were measured in an Electrothermal
melting-point apparatus and were uncorrected. Magnetic moment
measurement were performed according to the Evans NMR methods and
recorded in toluene solution at 306 K on a JOEL 60 MHz NMR spectrometer.
Elemental analysis (C, N, H) were conducted by MEDAC Ltd., Brunei
University, UK.
X-Ray Structural Analysis
Single-crystals of compounds 1，2，5-24 suitable for crystallographic
analysis were mounted in glass capillaries and sealed under nitrogen.
Diffraction data were collected on a Bruker SMART 1000 CCD diffractometer
using graphite-monochromatized Mo—Kcx radiation (X = 0.71073 A). The
structures were solved by direct phase determination using the computer
program SHELX-97 and refined by full-matrix least-squares methods with
SHELXTL program. Anisotropic thermal parameters were assigned for the
non-hydrogen atoms.* Hydrogen atoms were introduced in their idealized
* sheldrick, G. M. SHELX-97] Package for Crystal Structure Solution and Refinement] Universiy of Gottingen:
Gottingeri, Germany, 1997.
125
positions and included in structure factor calculations with assigned isotropic
temperature factors.
126
Appendix 2
Figure A-1. 1H NMR spectrum of compound 1 [Li(L 1 )(TMEDA)].
Figure A-2. 13 C NMR spectrum of compound 1 [Li(L 1 )(TMEDA)].
Figure A-3. 1H NMR spectrum of compound 2 [Li(L2)(TMEDA)]_
Figure A-5. 1H NMR spectrum of compound 5 [Li(L 3 )(TMEDA)].
Figure A-7. 1H NMR spectrum of compound 6 [{Li(L 1 )(THF)} 2 ].
Figure A-8. 13 C NMR spectrum of compound 6 [{Li(L 1 )(THF)} 2 ].
Figure A-9. 1H NMR spectrum of compound 15 [Ni(L1)2].
Figure A-10. 13 C NMR spectrum of compound 15 [Ni(L1)2].
Figure A-11. 1 H NMR spectrum of compound 16 [Ni(L2)2].
Figure A-12. 1 3 C NMR spectrum of compound 16 [Ni(L2)2].
Figure A-13. 1 H NMR spectrum of compound 17 [Zn(L1)2].
Figure A-14. 13 C NMR spectrum of compound 17 [Zn(L1)2].
Figure A-19. 1 H NMR spectrum of compound 20 [{Cd(L 2 ) 2 } 2 (TMEDA)].
Figure A-20. 1 3 C NMR spectrum of compound 20 [{Cd(L 2 ) 2 } 2 (TMEDA)].
Figure A-21. 1 H NMR spectrum of compound 2 4 [Cu2(L 2 )2].
Figure A-22. 13C NMR spectrum of compound 24 [Cu2(L 2 )2].
127
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Appendix 3
Table A-1. Crystallographic data for compounds 1,2 and 5.
Table A-2. Crystallographic data for compounds 6-8.
Table A-6. Crystallographic data for compounds 18—20.
139
Table A-1. Crystallographic data for compounds 1，2 and 5.
2 5
！
Molecular formula C27H48IJN5 C21H40UN5 CsoHseLiNsSi
Molecular weight 449.64 369.52 521.83
^ . , . 0 0.50 x 0.40 x 0.30 x 0.20 x 0.50 x 0.40 x

Crystal s.ze, mm3 Q 3Q 0 .10 0.30
Crystal system Triclinic Monoclinic Triclinic

• • 睡
Space group P1 Rh/n P1
a, A 9.9514(1) 9.385(2) 10.3891(1)
b, A 11.8665(1) 19.120(4) 11.4529(1)
C ，A 14.0091(1) 13.698(3) 15.8010(2)
(3, deg 99.515(2) 91.852(5) 84.068(2)
Z 2 4 2
V, A 3 1423.9(3) 2456.6(10) 1704.9(3)
Density, g cnr 3 1.049 0.999 1.017
Abs. coefficient, mm_1 0.062 0.06 0.093
Reflection collected 9831 13099 11720
Unique data measured 6782 4313 8059

Obs. data w i t h / > 2 a 346y 2012 3433
W
Final R indices [I>2o = 0. 0691 = 0. 0 7 6 9 R 1

= 0 0677
.
wR2 = 0.1779 wR2 = 0.2153 wR2 = 0.1747
R indices (all data)9 R1 = 0.1328 R1 = 0.1494 R1 = 0.1629
wR2 = 0.2227 wR2 = 0.2820 wR2 = 0.2344

am : ZI I F o l - I F c l l /I I F o l ; wR2={l[w(Fo 2- Fc 2) 2] / I [ u < F o ) ] } 1 / 2
140
Table A-2. Crystallographic data for compounds 6 - 8 .
- - g
° f
Molecular formula C50H80U2N6O2 C46H72MnN60 C66Hn2Mn2Ni4
^ 0 0.50 x 0.40 x 0.50 x 0.40 x 0.40 x 0.30 x

Crystal size, mm3 Q 3Q 0 30 0 .20
Crystal system Monoclinic Monoclinic Triclinic
Space group P2、/c P2i/n P?
a, A 11.7223(19) 17.854(3) 11-5832(15)
b, A 11.6407(18) 13.661(2) 12.3575(15)
c, A 18.465(3) 18.983(3) 14.1578(19)
/3, deg 101.684(3) 96.374(3) 14.1578(19)
Z 2 4 1
A3 2467.4(7) 4601.5(12) 1806.6(4)
Density，g crrr 3 1.092 1.126 1.114
Abs. coefficient, mrrr 1 0.066 0.325 0.395
Obs.data w i t h / > 2 a 2470 4570 3912

W
I D . .. ^ R1 = 0.0661 尺 1 = 0.0605 R1 = 0.0642
Final R indices [ / > 2 a
C0] a wR2 = 0.1693 = 0.1519 wR2 = 0.1584
R indices (all data) 3 = 0.1202 尺 1 = 0.1190 R1 = 0.1099
wR2 = 0.2193 = 0.1964 wR2 = 0.1953

: XIIFol - IFcll/ZIFol； wR2={l[w{Fo 2- Fc 2) 2] / l[w[Fo)]} V2
141
e 10
Molecular formula C5i.5H84MnN6Si2 C3oH38FeN6 C52H9oFeN6OSi2
^ . . . o 0.50 x 0.40 x 0.50 x 0.40 x 0.40 x 0.30 x

Space group PT C2/c PI
仏 A 10.3366(19) 27.299(4) 10.2105(15)
b/fK 12.615(2) 8.2628(11) 12.1593(18)
C，A 22.625(4) 16.386(2) 24.815(4)
/3, deg 102.726 117.660(2) 80.305(2)
Z 2 4 2
V, A3 2728.5(9) 3273.8(8) 2807.3(7)
Density，g crrv3 1.093 1.113 1.097
Abs. coefficient, mnr 1 0.323 0.487 0.35
Obs. data w i t h / > 2 a 51QQ 2680 6884
W
Final R indices [ / ^ 2 a 尺1 = 。細 ^ = 0.0467 = 0.0545
(J)] a W R2 = 0.1633 w^ = 0.1276 wR2 = 0.1399
R indices (all data)3 R1 = 0.1242 尺1 = 0.0753 R1 = 0.0832
W R2 = 0.2066 wR1 = 0.1469 wR2 = 0.1639

= IIIFol - IFcll/IIFol； wR2={l[w(Fo 2- Fc2)2] / l[w[F0)]y /2
142
Table A-4. Crystallographic data for compounds 12—14.
- - -
Molecular formula C42H63C0N6 C30H48C0N6 C48H8oCoNeSi2
^ . , . . 0.50 x 0.40 x 0.50 x 0.30 x 0.40 x 0.30 x

Crystal system Triclinic Monoclinic Monoclinic
Space group PT C2/C P2i/n
A 12.1841(18) 27.171(12) 8.946(2)
A 12,2852(18) 8.262(4) 14.117(3)
Cj A 14.498(2) 16,380(7) 19.858(4)
p, deg 102.199(3) 118.028(7) 95.990(4)
Z 2 4 2
Vj A3 2083.7(5) 3246(2) 2494.4(10)
Density, g crrv3 1.133 1,129 1.14
Abs. coefficient, mm"1 0.446 0.555 0.429
Obs. data w i t h / > 2 a 3864 2542 3936

W
， ^ .」. rr 0 R1 = 0.0762 R1 = 0.0539 R1 = 0.0596
Final R indices [I>2o
WR2 = 0.2010 wR2 = 0.1447 wR2 = 0.1529
R indices (all data)3 尺 1 = 0.1899 = 0.0900 R1 = 0.0935
wR2 = 0.2737 wR2 = 0.1736 wR2 = 0.1790

am : I I I F o l 一 I Fcll 1 IIF o l ； wR2={2[w{Fo 2- F c
2
) 2
] 1 l[w[F0)]y /2
143
Molecular formula C42H64N6Ni C3oH48N6Ni C42H64N6Zn
^ . , . o 0.50 x 0.30 x 0.40 x 0.30 x 0.40 x 0.30 x

Space group PT C2/m R\
A 10.1899(16) 17.742(2) 12.142(2)
b) A 17.820(3) 10.9389(15) 12.3325(19)
C，A 24.387(4) 8.1470(11) 14.315(2)
p, deg 95.491(3) 99.357(2) 101.444(3)
Z 4 2 2
Fj ^3 4107.3(11) 1560.1(4) 2067.5(6)
Density, g crrr 3 1.151 1.174 1.154
Abs. coefficient, mrrr 1 0.507 0.649 0.629
Obs. data w i t h / > 2 a 7Q30 1798 4390

W
「. ， n . r r n m = 0.0653 R1 = 0.0547 = 0.0736
Final R indices [ / > 2 a
C0]a wR2 = 0.1532 wR1 = 0.1490 wR2 二 0.1841
R indices (all data)3 = 0.1343 R1 = 0.0622 m = 0.1662

= 0.1972 i/vR1 = 0 . 1 5 5 8 wR2 = 0 . 2 4 0 1
: ZIIFol - IFcll/IIFol； wR2={Z[w(Fo 2- Fc 2) 2] / I[n<F 0 )]} 1/2
144
18 19 20
Molecular formula C3oH48N6Zn C48HsoN6Si2Zn C66H112CCI2N14
^ . . . 0 0.40 x 0.30 x 0.50 x 0.40 x 0.50 x 0.40 x

Crystal system Monoclinic Triclinic Triclinic
Space group C2/c PI P\
A 27.250(4) 10.235(3) 11.5745(18)
A 8.2689(12) 12.731(4) 12.686(2)
C，A 16.472(2) 22,456(7) 14.141(2)
fS, deg 118.028(2) 90.242(5) 87.394(3)
Z 4 2 1
K ^3 3276.3(8) 2689.7(14) 1844.4(5)
Density，g cm' 3 1.132 1.064 1.194
Abs. coefficient, mm_1 0.776 0.535 0.622
°bs- data with 1 ^ 2 G 2887 7754 4898

⑵
Final R indices [ I > 2 a 尺1 = 0 . 0 4 6 7 尺1 = 0 . 0 4 0 3 R1 = 0.0606
C0]a wR2 = 0.1212 wR2 = 0.1115 wR2 = 0.1702
R indices (all data) 3 尺 1 = 0.0693 尺 1 = 0.0509 = 0.0797
wR2 = 0.1350 wR2 = 0.1163 wR2 = 0.1836

-m = IIIFol - IFcll 1 XIFol； WR2 = {l[w{Fo 2 一 Fc2)2] 1 l[w(F0)]y /2
145
^ ‘ . 仏 c ' h ；： / - 1 , '^Mmm 圓釋導 … 零
21 22
Molecular formula CaoHseCIMnNsSi C3oH56CIFeN5Si
Molecular weight 605.28 606.19
Crystal size, mm 3 0.50 x 0.40 x 0.30 0.50 x 0.40 x 0.30
Crystal system Monoclinic Monoclinic
Space group P2i/c P2i/c
a 、k 20.19(2) 20.205(3)
bj A 15.528(16) 15.464(3)
c，A 22.08(3) 22.097(4)
/3, deg 93.29(2) 92.973
Z 8 8
^3 6911(13) 6895(2)
Density, g cnr 3 1.164 1.168
Abs. coefficient, mnr 1 0.519 0.575
Reflection collected 34958 46494
Unique data measured 12153 16658
Obs. data w i t h / > 2 a ( 7 ) 5280 6445

R1 = 0.0536 R1 = 0.0580
Final R indices [I>2o(I)] a
wR2 = 0.1307 wR2 = 0.1344
R indices (all data) 3 尺 1 = 0.1453 尺 1 = 0.1932
wR2 = 0.1863 wR2 = 0.1983

= IIIFol 一 IFcll 7 IIFol； wR2 :{I[ia<FO 2 - F c 2 ) 2 ] 1 I N W ^
146
- -
Molecular formula CaiHsgMnNsSi C30H48CU2N6
Molecular weight 605.28 619.82
Crystal size, mm 3 0.50 x 0.40 x 0.30 0.40 x 0.30 x 0.20
Crystal system Monoclinic Monoclinic
Space group P2i/c C2/c
"，A 20.19(2) 18.451(4)
bj A 15.528(16) 16.202(4)
Cj A 22.08(3) 12.878(3)
/3, deg 93.29(2) 121.795(4)
Z 8 4
Fj ^3 6911(13) 3272.2(13)
Density, g cm*3 1.164 1.258
Abs. coefficient, mrrr 1 0.519 1.327
Reflection collected 34958 10874
Unique data measured 12153 3950
Obs. data w i t h / > 2 a (7) 4713 2879

R1 = 0.0536 R1 = 0.0398
a
Final R indices [I>2o(I)]
wR2 = 0.1307 wR2 = 0.1063
R indices (all data)3 尺 1 = 0.1453 = 0.0620
wR2 = 0.1863 wR2 = 0.1216

: III F o l - I F c l l /I I F o l ； wf=l2={l[w(Fo 2- Fc 2) 2] / l[w[F0)]y /2
147
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Synthesis and Structural Characterization of Divalent

Metal Complexes Supported by Guanidinato Ligands

YEUNG, Lai Fong

A Thesis Submitted in Partial Fulfilment

of the Requirements for the Degree of

The Chinese University of Hong Kong

Professor XIE, Zuowei (Chair)

Professor LEE, Hung Kay (Thesis Supervisor)

Professor LEUNG, Wing Por Kevin (Committee Member)

Professor CHAN, Wai Kin (External Examiner)

The present research work focused on the coordination chemistry of

guanidinate ligands of the general formula [(C6H3Me2-2，6)NC(N(RR，)N(F^]-. The

structural characterization and reactivity of mono(guanidinate) metal complexes.

Chapter One gives a brief review on guanidinate metal complexes.

Chapter Two describes the synthesis and structural characterization of the

newly developed unsymmetrical guanidinate ligands

[(C6H3Me2-2，6)NC(NRR，)NR，]-[ R = CeHu, R，= H (L1); R = C 3 H 7 , R ' = H (L2); R

= C e H u , R' = SiMe3 (L3)]. Bis(guanidinate) complexes of the first-row divalent

successfully prepared by metathesis reactions between MCI2 (M = Mn, Fe, Co,

Monomeric [M(L 1 ) 2 (THF)] (7)，[M(L1)2] [M = Co 12，Ni 15，Zn 17]，[M(L 2 ) 2 ] [M =

synthesized. Binuclear [{M(L 2 ) 2 } 2 (TMEDA)] [M = Mn 8，Cd 20] were also

isolated. Effects of the steric bulkiness of the guanidinate ligands on the

structure of the corresponding metal complexes were examined.

Chapter Three reports on the preparation and structural characterization of

mono(guanidinate) metal complexes supported by the [(CeH3Me2-2，6)NC(N(Cy)

(SiMe3))NCy]_ (L3) ligand. Mono(guanidinate) complexes of Mn(ll) and Fe(ll)

Mn 21，Fe 22] were synthesized. Reaction of [Mn(L 3 )(TMEDA)(CI)] (21) with

LiMe led to the corresponding Mn(ll) guanidinate-methyl complex [Mn(L 3 )

(TMEDA)(Me)] (23). Copper(l) mono(guanidinate) complex [Cu 2 (L 2 ) 2 ] (24) was

also prepared and structurally characterized.

C 6 H h , R ' = H (L 1 ); R = C3H7 R' = H (L 2 ); R = C 6 H N , R，= SiMe 3 ( L 3 ) ] 的 合 成 和 結

法合成了十二個單節顯性的雙（胍基）金屬配合物：[M(L 1 ) 2 (THO] (7)，[M(L1)2]

[M = Co 12，Ni 15，Zn 17]，[M(L2)2] [M = Fe 10，Co 13，Ni 16, Zn 18]和[M(L 3 ) 2 ]

[M = Mn 9，Fe 11，Co 14，Zn 19]，和兩個兩核的雙（ 胍基）金屬配合物：

[{M(L 2 ) 2 } 2 (TMEDA)] [M = Mn 8，Cd 20]。另外，亦會描述胍基配體上的烷基取代

第三章講述採用胍基配體[(C 6 H 3 Me 2 -2，6)NC(N(Cy)(SiMe 3 ))NCy]- (L 3 )所合成的

(金屬：錳、鐵）和相同的摩爾分子量的鋰鹽[Li(L 3 )(TMEDA)] (5)進行反應，產

生了二個單節顯性的單（胍基）金屬配合物：[M(L 3 )(TMEDA)CI] [M = Mn 21，Fe

22]。單（胍基）錳配合物[Mn(L 3 )(TMEDA)(CI)] (21)與甲烷基鋰鹽進行甲基化作

用，合成單胍基-甲基錳配合物[Mn(L 3 )(TMEDA)(Me)] (23)。另外，一價的單（ 胍

I would like to express my sincere thanks to my supervisor,

and the preparation of this thesis.

I am indebted to Prof. MAK, Chung Wai Thomas and Miss

CHEUNG, Yu Sun for the assistance of magnetic moment

My deepest gratitude goes to my labmates, Miss YAO,

their wholehearted support in these two years. I would like to give

my sincere gratitude to my dearest friends, Miss LAM, Hoi Yi, Miss

Ki Jay for their continuous encouragement.

Finally, my immense gratitude should go to my beloved

family for their countless love and support.

YEUNG, Lai Fong

Chapter One 一 Introduction

1.2 General Background of Guanidinates 2

1.3 Coordination modes of Guanidinate Ligands 5

1.4 A Brief Review on the Coordination Chemistry of Guanidinate

1.4.1 Main Group Metal Guanidinate Complexes 7

1.4.2 Transition Metal Guanidinate Complexes 12

1.4.3 Rare Earth Metal Guanidinate Complexes 13

1.5 Preparations of Metal Guanidinate Complexes 15

1.6 Applications of Guanidinate Complexes 16

1.7 Objectives of This Work 18

1.8 References for Chapter One 19

Chapter Two 一 Synthesis and Structural Characterization of

2.1.1 Guanidinate Complexes of the Alkali Metals 25

C 6 H h , R ' = H (L 1 ); R = C3H7 R' = H (L 2 ); R = C 6 H N , R，= SiMe 3 ( L 3 ) ] 的合成和結

[M = Mn 9，Fe 11，Co 14，Zn 19]，和兩個兩核的雙（胍基）金屬配合物：

用，合成單胍基-甲基錳配合物[Mn(L 3 )(TMEDA)(Me)] (23)。另外，一價的單（胍