Syntheses and Structures of Copper and Zinc Complexes with ...

Syntheses and Structures of Copper and Zinc Complexes with

N � 0 Donor Ligands

by

CHAN Sau Han

A thesis submitted in partial fulfillment of the requirements

for the degree of Master of Philosophy

in Chemistry

© The Chinese University of Hong Kong August 2001

The Chinese University of Hong Kong holds the copyright of this thesis. Any person(s) intending to use a part or whole of the materials in the thesis in a proposed publication must seek copyright release from the Dean of the Graduate School.

统系書口 \ 气

I [ " 婦 • ) i

N pXlibrary

Thesis Committee:

Prof. Wai Kee L I

Prof. Thomas C. W. MAK

Prof. Hung Kay LEE (Supervisor)

Prof. Xiao-Ming CHEN (External Examiner, School of Chemistry and

Chemical Engineering, Zhongshan University)

ABSTRACT

This thesis describes the syntheses, structures and characterization of a series of

copper and zinc complexes derived from tripodal tetradentate N3O ligands,

containing phenolate pendants.

Chapter 1 gives a general introduction to the roles of copper in biological

systems. The chemistry of radical-copper proteins is also introduced.

Chapter 2 describes the syntheses and characterization of a series of

monomeric copper(II) and analogous zinc(II) complexes of the type [M(L)(X)] (M =

Cu, Zn; X = OAc, CI), where L being pyridine-based tripodal tetradentate N3O donor

ligands containing phenolate pendants. Subsequent oxidation of these complexes

with cerium(IV) ammonium nitrate has been studied.

Chapter 3 describes the syntheses and characterization of several novel mono-

and dimeric copper(I) complexes containing benzimidazole- and pyridine-based

tripodal tetradentate N3O donor ligands. The reactivities of these complexes toward

dioxygen have also been investigated.

Chapter 4 gives the experimental details of compounds described in the

preceding chapters.

i

摘要

本論文敘述了一系列由利三氮單氧四齒配體配位的具有三角支架特點的銅

鋅絡合物的合成、鑒定及結構特性。

第一章敘述了銅配合物在生物體內的作用，同時，還對自由基銅蛋白化學

進行簡要介紹。

第二章敘述了由卩a：卩定衍生的包含酌驢側基的三氮單氧四齒配體配位、具有

三角支架特點的單聚銅鋅絡合物[M(L)(X)] (M = Cu, Zn; X = OAc, CI)

的合成及鑒定o同時’還對該類絡合物在确酸鈽錢作用下的氧化反應進行了硏

究°

第三章敘述幾個新型的由苯并咪嗖和rtfc卩定衍生的三氮單氧四齒配體配位具

有三角支架特點的單聚和二聚的一價銅絡合物的合成及結構鑒定，還對該類絡

合物跟雙氧的氧化反應進行了硏究。

第四章敘述了以上各章的實驗步驟。

ii

ACKNOWLEDGMENT

I would like to express my sincere thanks to my supervisor, Prof. Hung Kay

LEE for his advice and guidance in my research work and in the preparation of this

thesis.

Thanks are given to Dr. Yee Lok WONG for his special contribution and

helpful discussion on my research project.

I would like to express my sincere gratitute to Dr. Tze Lock CHAN for

providing me a bench space in the first year of my M.Phil, study.

We thank Prof. Sunney L Chan, Vice-President of Academia Sinica, Taiwan,

for provision of a low-temperature accessory for taking all low-temperature UV-Vis

spectra. Thanks should also go to Dr. Svetlana Pavlova of the Institute of Chemistry

at Academia Sinica for her assistance in taking low-temperature UV-Vis spectra.

Thanks are also due to Prof. Thomas C. W. MAK and Miss Hung Wing L I for

carrying out all X-ray crystallographic analyses, and Mr. Kwok Wai KWONG and

Mr. Chung Hei LAM for measuring all mass spectra.

Special thanks are given to Dr. Chunmei WAI, Dr. Gulice Y. C. LEUNG, Mr. <i

Jie JIANG，Mr. Guo Xin WONG, Mr. Kai For MO, Mr. Leung HOU, Dr. Stanton H.

L. KWOK and all the group members for their helpful discussion.

Sau Han CHAN

Department of Chemistry

The Chinese University of Hong Kong

July, 2001.

iii

CONTENTS

Page

ABSTRACT i 摘要 i i

ACKNOWLEDGMENT iii CONTENTS iv ABBREVIATIONS vi

CHAPTER 1 General Introduction 1-A. Role of Copper in Biology 1

1-B. A Brief Review on Radical Copper Proteins 4

1-C. Objectives of This Work 12

1-D. References 13

CHAPTER 2 Copper(II) and Zinc(II) Complexes containing N3O Tetradentate Ligands 2-A. Introduction 14

Results and Discussion

2-B. Preparation of Tetradentate Ligands and 27

Complexes

2-C. Characterization 36

2-D. Generation of Metal Phenoxyl Radical Species 51

2-E. Summary 57

2-F. References 59

CHAPTER 3 Copper(I) Complexes with N3O Tetradentate Ligands 3-A. Introduction 62


3-B. Preparation of Copper(I) Complexes with N3O 75

Tetradentate Ligands

iv

3-C. Characterization 79

3-D. Reactivities of 86，87 and 88 toward Dioxygen 88

3-E. Summary 93

3-F. References 94

CHAPTER 4 Experimental Sections 4-A. General Preparations and Physical 97

Measurements

4-B. Compounds Described in Chapter 2 99

4-C. Compounds Described in Chapter 3 113

4-D. Oxo-Transfer to Triphenylphosphine as 117

Described in Chapter 3

4-E. References 119

APPENDIX A 1h and NMR Spectra A-1. Compounds Described in Chapter 2 120

A-2. Compounds Described in Chapter 3 127

APPENDIX B Crystallographic Data B-1. X-ray Crystal Structure Data for Complexes in 131

Chapter 2

B-2. X-ray Crystal Structure Data for Complexes in 133

Chapter 3

APPENDIX C GC-MS Spectra C-1. GC-MS Spectra for Standard Samples 134

C-2. GC-MS Spectra for the Reactions with 136

Triphenylphosphine Described in Chapter 3

V

ABBREVIATIONS

°C degree Celsius min. minute(s)

d chemical shift in parts per mol. mole(s)

million downfield from mp melting point

tetramethylsilane (spectral) MS mass spectrometry

Anal. analysis m/z mass to charge ratio

Ar aryl M+ molecular ion

br broad (spectral) NMR nuclear magnetic resource

/-Bu tert-butyl Ph phenyl

calcd. calculated ppm parts per million

cone. concentrated Py pyridine

d doublet (spectral) q quartet (spectral)

dec. decomposed r.t. room temperature

DMSO dimethylsulfoxide s singlet (spectral)

EI electron impact solv. solvent

Et ethyl t triplet (spectral), tertiary

EXAFS extended X-ray absorption THF tetrahydrofliran

fine structure TMS tetramethylsilane

FAB fast atom bombardment

g gram(s)

HRMS high resolution mass

spectrometry

Hz hertz

h hour(s)

J coupling constant

LSI liquid secondary ion

m multiplet (spectral), milli-

Me methyl

vi

CHAPTER 1

General Introduction

l-A. Role of Copper in Biology

Copper has been known to be an essential element in biological systems since

1925.1 With a rapid development in trace element analysis, protein crystallography,

spectroscopy, and molecular biology in the last two decades, the biological relevance

of copper has been d i sc losed ,� The emergence of bioinorganic chemistry has

created an interaction between inorganic chemistry and various aspects of biology,

providing insights to the understanding of the roles of copper in various biological

systems.

The occurrence of two oxidation states, viz. +1 and +2, renders copper to be an

important cofactors in a number of redox proteins, electron-transfer proteins, and

dioxygen carriers. Apart from these, copper is also an important element in a

number of non-organometallic redox catalysts, e.g. in organic syntheses and

industrial processes (Figure I ”

Although copper is an important element in biology, detailed information of its

biological functions has not been completely understood. From a structural and

spectroscopic point of view, three main types of copper centers, namely Type 1，Type

1

2，and Type 3，are classified in biological systems (Table 1).4，5 By now, corelations

with analytical features such as optical absorption, electron paramagnetic resonance

spectroscopy, and magnetism have been largely understood due to an increase in

available structural and spectroscopic information. Recent studies have established

several special combinations (e.g. Type 2+3 trimer. See Table 1) and other copper

centers such as C u a and MT-Cu.

JCXq 一 melanins

2 。 2 + i 7 JOC0H+H2O O22- + 02 RCH2NH2 + 02

2 RCHO + H2O2 + NH3

tyrosinase HO o CO + depsid i / ^ ^ ^

I 、 i . a s c o r b a t e . O ,

h c T ^ ^ c ^ Y " ^ +O2 — V r S ^ ^ ^ ^ dehydroascorbate + 2H2O

r ； N2 + H z O ^ N2O r e d u c t a s e ^ 广 . • ^"^^^blue' copper proteins ® , , , 、

) 。 U (C (electron transfer)

NCV / gaactose 、H2O

。 2 l P h 。矿 +02 (dioxygen transport) O2 OH

RCHO RCH2OH Y y ^ +H0O + + HO-^ 2

H2O2 H2O Figure 1. The essential metabolic functions of copper-containing proteins are summarized in the 'bicopper dial'. The close association of this bioelement with dioxygen and its secondary products is obvious. Not included are transport, regulatory, and storage proteins for copper.

2

Tabl

e 1.

Pro

perti

es o

f var

ious

bio

logi

cal c

oppe

r cen

ters

.

Type

1 Ty

pe 2

Type

3 Ty

pe (2+

3) trim

er C^

MT

-Cu

Aggre

gation

state

monon

uclear

mo

nonucl

ear

dinucl

ear

trinucl

ear

dinucl

ear

monon

uclear

to

multi-

nuclea

r Sp

ecific

ity, b

io-

electr

on tra

nsfer

cataly

sis an

d redo

x O2

activ

ation f

or O2

activ

ation f

or ele

ctron

transf

er reg

ulatio

n, sto

rage,

logica

l funct

ion

reactiv

ity

transp

ort an

d oxi

dase f

uncti

on and

transp

ort fo

rm

oxygen

ation

Occur

rence

'blue'

coppe

r prot

eins a

mine

oxidas

e, hem

ocyani

n, asc

orbate

oxida

se,

N2O

reduct

ase，

CU

P2, m

etallo

-(ex

ample

s) gal

actose

oxida

se,

tyrosi

nase

laccas

e cyt

ochrom

e c

thione

in (M

T), Cu

sup

eroxid

e dis-

oxidas

e tra

nsport

ATP

ase

mutas

e, cyto

chrom

e c

oxidas

e Str

uctura

l char

acteri

stics

typica

l coor

din-

3 (trig

onal-p

lanar)

4 o

r 5 (s

quare-

planar

Cu丨：

3 (trig

onal-

Cu丨：

3 (trig

onal)

4 3 (

trigona

l-plan

ar)

ation n

umber

or

-pyram

idal)

planar

) Cu

": 4

coordi

nated

atoms

S"

(Cys")

, 2 N

(His),

3 N

(His)

# 2x3

N (H

is); Q

jH:

N (H

is), pa

rtly

2 S" (C

ys"),

3 S"

(Cys*)

S (

Met)

'-Oi

(0)0H

- 2 N

(His),

S (M

et)

or O

(pepti

de)

Spectr

oscopi

c char

acteri

stics o

f the o

xidize

d or o

xygena

ted fo

rm

EPR

small

"Cu/^

'Cu

‘norma

l，Cu"

EPR

no sig

nal (s

trong

‘norma

l，Cu"

EPR

very s

mall C

u no

oxidiz

ed for

m hyp

erfme

splitt

ing

param

eters

antipa

rallel

spin-s

pin p

arame

ters

hyper

fme s

plittin

g (A/

/)’ low

g fac

tor (g

") cou

pling)

due

to tw

o equi

valent

Cu

, low g

facto

r ligh

t absor

ption

intens

e abso

rption

in n

o inte

nse ab

sorp-

intens

e abso

rption

; int

ense a

bsorpt

ion;

absorp

tion i

n the

near

t^e vi

sible

LMCT

tion，

only

LMCT

((-一

匚！！之十）

LMCT (

(V.—

Cu?,

infrar

ed reg

ion

(Cys-

—Cu2

� ‘fo

rbidde

n, lig

and

(MMC

T) fie

ld tra

nsitio

ns fre

e coor

dinatio

n site,

speci

al lig

ands (o

rganic

radic

als), o

r adja

cent m

etal c

enters

(Zn,

Fe).

“

1-B. A Brief Review on Radical Copper Proteins

In recent years, studies of protein systems containing metal-radical arrays have

7 8

attracted considerable interest.， As shown in Figure 1，three types of copper-

containing enzymes, namely, galactose oxidase (GAO), copper amine oxidase (CAO)

and dopamine monooxygenase (D/3M) have been known to catalyze the

oxidation of substrate by involving a metal-radical species in their catalytic cycles/

Among these copper enzymes, galactose oxidase (GAO) is the one that received the

most extensive studies. GAO is a secretory fungal enzyme which has been isolated

from culture filtrates of Dactylium dendroides, Gibberella fujikuroi, and Fusarium

graminearum^ This enzyme is monomeric with a relative molecular mass of 68

kDa. It catalyzes the two-electron oxidation of galactose (and a broad range of

primary alcohols) to the corresponding aldehydes together with a concomitant

formation of hydrogen peroxide. It is noteworthy that the enzyme catalyzes the

oxidation of alcohols in a regioselective, but not substrate-specific manner (Eq.l).4

CH2OH CHO 0 \ y \ 0 \ 0 H OH/^ O OH N O H i ^ + 〇2 X O H i ^ + H2O2

OH OH

R-CH2OH + O2 R-CHO + H2O2 (Eq 1)

4

In fact, the biological role of the enzyme is not fully understood. One possible

function of this enzyme is degradation of rotting wood by oxidation of

oligosaccharide intermediates, which are preferred substrates of the enzyme.

Besides, the coupled formation of hydrogen peroxide is also important as it serves as

a bacteriostatic agent and an essential cosubstrate for peroxidases

The catalytic mechanism on how GAO catalyzes the oxidation of substrates has

been a controversial topic over years. In 1978，Hamilton et al suggested a reaction

mechanism which involved a redox pair.^^ However, with detailed

spectroscopic and magnetic studies of the enzyme, together with a recent report on

its crystal structure, a catalytic mechanism for the enzymatic turnover has been

proposed (Figure 2)}^

5

Tyr495

His496 ^ ― ( .His581 His496 V " ' ^ xHis581

)= \ 9 /=< >=\ \ r=\ Active form . c u T 一 . c u T 一

r A ' H 尸 FA""H / H ^ ^ H ^

^ ‘ Cys228 Cys228

O2 + RCH2OH ) H atom abstraction 广 H2O2 + RCHO

1 r 丁 y r ^ Tyr495

Q , Q His49a. (？^ /His581 His496 .His581

> = \ i / = \ > = \ [ / = \ H N ^ N v ： Z*、N^NH H N ^ N v ^ i ^ N ^ ^ N H

Reduced form ^ c ' ^ 一

Cys228 (^s228

Figure 2. Proposed catalytic mechanism for galactose oxidase.

The active site of the enzyme consists of a mononuclear copper ion in a square-

pyramidal coordination geometry (Figure 3). At pH 7.0，the copper ion is

coordinated to two histidine residues (His 496, His 581), a tyrosine residue (Tyr

495)，a water molecule (which is replaced by an acetate ion in acidic media), and a

cysteinate-substituted tyrosine residue (Tyr 272) of which the ortho position is linked

to a cysteinate side chain (Cys 228). This arrangement is believed to stabilize the

corresponding tyrosyl radical by lowering its redox potential and allowing for spin

delocalization. Another feature that help to stabilize such radical species is the

6

presence of the tryptophan residue, Tip 290. The indole part of which, being located

ca. 3.4 A above the cysteinate-substituted tyrosine residue, is believed to exert a

stabilizing effect to the tyrosyl radical through a t t to t t stacking interaction.

Tyr495

5 8 1 H i s ^ \ j N I

H N ; 2 N Z 、〇 s〉

产 acetate or Cys228 His496 water

Figure 3. A schematic view of the active site of galactose oxidase in its inactive form.

Copper amine oxidase (CAO) belongs to a family of quinoproteins. It catalyzes

a two-electron oxidation of primary amines to the corresponding aldehydes, with the

formation of a reduced form of the cofactor. Subsequently, the reduced cofactor is

reoxidized by oxygen, resulting in the formation of both ammonia and hydrogen

peroxide. Such reactions can be formally divided into a reductive and an oxidative

half-reaction (Eq. 2 and 3).

7

Reductive half-reaction:

0 OH G ^ o r r V N H 2

:少 + RCH2NH2 • I . + RCHO

^ ^ (Eq. 2)

Oxidative half-reaction:

OH O

1 J + O2 + H2O • X J + H2O2 + NH3

^ ^ (Eq. 3)

CAO can be isolated in bacteria, yeast, plants, and mammals. It plays an

important role in the regulation of biogenic amine levels through oxidative

metabolism. However, the exact number, location, and regulation of this enzyme in

cells remain unclear. This enzyme is dimeric in nature with each monomer

consisting of a 75-80 kDa polypeptide, each of which contains a single curpic ion7

The copper center in the active site is ligated by three histidine residues (His 442, His

444, and His 603) and two water molecules in a distorted square-pyramidal

coordination geometry. Besides, an organic cofactor, 2,4,5-trihydroxyphenylalanine

(TPQ) is also present. X-Ray crystallography revealed that the latter cofactor is

located close to the copper center. Figure 4 depicts a proposed catalytic mechanism

for CAO.8

8

⑷ RCH2NH2 H20

^ X c u " " I V > ^ T^

裕 V U % V 0 Asp/Glu 0 H

1 r RCHO H2O

1 / I fast J L I o h R h o

OH O一 H

(b)

7—— , ~ O2 , — — ， - i • • O s ^

cull C u i Y V ^ N H , OH OH OH

n h ^ r " " ' t i ^ Cu" ^ o Cu" \ A S H 2

-O 一 0 O

Figure 4. Proposed mechanism for copper amine oxidase: (a) reductive half-reaction, (b) oxidative half-reaction.

As GAO and CAO are specific for the oxidation of primary alcohols and

amines, respectively, considerable interests have been attracted to these enzymes for

biosensor applications.

9

Dopamine 曰 monooxygenase (D/3M) catalyzes the conversion of neuro-

transmitter dopamine to norephinephrine (Eq. 4).^ Therefore, this enzyme plays an

important role in controlling the levels of these neurotransmitters in higher

organisms.

OH

_ ascorbate i + O2 • I ^ + H2O

H O " H C A ^ (Eq.4)

During enzymatic turnover, an oxygen atom is inserted into the benzylic

position of the ethylamine side chain of dopamine (or other phenethylamine

analogues), with a concomitant four-electron reduction of oxygen to water. Two of

these electrons originate from the substrate, while the other two come from the

exogenous electron donor, ascorbic acid. The latter undergoes oxidation in two

sequential steps to produce semidehydroascorbate^

Interestingly, D/5M contains two coppers in each subunit. One of the copper

center exits in an active dimeric form while the other one exits in a tetrameric form.

These two copper centers are separated by 4 A apart. However, they can be

categorized as mononuclear copper proteins because these two copper centers

10

perform different functions during the enzymatic turnover. One of them, C u a ,

catalyzes an electron transfer from ascorbate to the active site, while the other one,

Cub, catalyzes the hydroxylation of the substrate. In 1994, Klinman and co-workers

proposed a mechanism for the C u b site (Figure 5) which involves a tyrosyl radical in

the hydroxylation of dopamine. ^ However, no direct evidence has been obtained to

support this model.

广 H20 CUB(II) / f J ^

\ V ^ CUB\(") L J U i、u X O T CUB(II) H.. T 、H H/0 H H + .0 ..。• + 乂 7NH3 •

Ar〜NH3 Ar 〜 Ar〜NH3

T X — - v V A r 二 N 、

Figure 5. Proposed mechanism for dopamine 曰 monooxygenase in substrate hydroxylation.

11

1-C. Objectives of This Work

The first part of this research work focuses on model studies of the copper-

containing protein, galactose oxidase (GAO). A series of copper(II) and zinc(II)

complexes of the type [M(L")(X)] (M = Cu, Zn; X = OAc，CI), where V being N3O-

type tripodal tetradentate ligands containing phenolate pendants, have been

synthesized as mimics to the active center of GAO. Subsequent oxidation of some of

these complexes with cerium(IV) ammonium nitrate gave the corresponding copper-

phenoxyl radical species, which are thermally stable only at low temperatures. The

model complexes and the corresponding oxidized radical species have been

characterized by EPR and UV-Vis. They elicit similar spectroscopic properties as

those observed for the native enzymes.

The second part of this work deals with the chemistry of copper(I) complexes.

Copper(I) complexes of the type [M(HL”)（ -I)]2 and [M(HL”)I] have been prepared

and structurally characterized. Their reactivities toward dioxygen have also been

investigated.

12

1-D. References

1. Linder，M. C.; Goode, C. A. Biochemistry of Copper, Plenum, New York, 1991.

2. Karlin, K. D.; Tyeklar，Z. Bioinorganic Chemistry of Copper, Chapman & Hall,

New York，1993.

3. Lippard, S. J.; Berg, J. M. Principles of Bioinorganic Chemistry, University

Science Books, Mi l l Valley, 1994.

4. Kaim, W.; Rail, J. Angrew. Chem. Int. Ed. Engl 1996，35, 43-60.

5. Solomon, E.; Baldwin, M. J.; Lowery, M. D. Chem. Rev. 1992, 92, 521.

6. Stubbe, J. Biochemistry 1998，27, 3893-3900.

7. Klinman, J. P. Chem. Rev. 1996, 96, 2541-2561.

8. Stubbe, J.; Donk, W. A. Chem. Rev. 1998，98, 705-762.

9. Whittaker, M. M.; Whittaker, J. W. J. Biol Chem. 1988，263, 6074-6080.

10. Whittaker, M. M.; Ballou, D. P.; Whittaker, J. W. Biochemistry 1998，57, 8426-

8436.

11. Hamilton, G. A.; Adolf, P. K.; De Jersey, J.; DuBois, G. C.; Dyrkacz, G. R.;

Libby，R. D. J. Am. Chem. Soc. 1978，100, 1899-1912.

12. Ito, N.; Philips, S. E. V.; Stevens, C.; Ogel，Z. B.; McPherson, M. J.; Keen, J. N.;

Yadav, K. D. S.; Knowles, P. F. Nature 1991, 350, 87-90.

13

CHAPTER 2

Copper(II) and Zinc(II) Complexes containing N3O Tetradentate Ligands

2-A. Introduction

2-A-I. The Active Site Structure of Galactose Oxidase

In recent years, the structures, spectroscopic properties, and catalytic mechanism

of GAO have been extensively studied. Ito and co-workers have reported the crystal

structure of GAO at 1.7 人 resolution. The protein crystals were obtained from an

acetate buffer (0.8 M) at pH 4.3 - 4.7 in the presence of the precipitant, ammonium

sulfate. The structure was consistent with the information from spectroscopic

studies. The copper active site is coordinated by five ligands in a square pyramidal

coordination geometry. The equatorial positions are occupied by Tyr 272，His 496，

His 581，and a water molecule or an acetate ion, whilst the axial position consists of

Tyr 495 (Figure 6 ) }

Electron paramagnetic resonance, optical absorption, and circular dichroism

studies of GAO have been carried out by Whittaker and co-workers.^ The EPR

spectra consist of a typical copper signal with g// = 2.28 and g丄=2.05.2 The optical

14

absorption spectrum is dominated by an intense absorption feature at 445 nm and a

broad one extending into the near infrared region with a maximum at around 900

nm.3

Tyr495

His496^ O His581

r ^ 2.69 A f = \ h n ^ N , . .N^NH

2.11 A...Cu".么 15 A 2.27-2.80

O ^ ― T y r 2 7 2 acetate or __(J water /

s〉

Cys228

Figure 6. Schematic view of the active site of galactose oxidase.

Circular dichroism spectra of the protein were recorded in a redox buffer over a

range of potentials. Significant features are crossing points at 337，356, 390 and 587

nm, and the convergence point at 493 nm. A few relatively intense circular

dichroism features, corresponding to three transitions, were observed in the visible

region at 490，620 and 770 nm. These remarkable absorption features provide

further information on the active site of the native enzyme.^

15

2-A-II. Biomimetic Models for Galactose Oxidase

A variety of metal complexes are synthesized as mimic to the active site of

various metalloenzymes in order to understand their structures and catalytic

mechanisms. However, most of these model complexes serve only as structural

models and very few of them show catalytic reactivities similar to those of the native

enzymes. Thus, biomimetic models that mimic both structure and function of an

enzyme remain rare.

Stack and co-workers have prepared a series of copper(II) complexes with non-

square planar N2O2 donor ligands (Scheme 1).4 It is believed that the binaphthyl

unit of the ligands can enforce a non-square planar coordination geometry, which is

OH o 1- TMEDA. EtOH, 25°C OH O

I ^ A y ^ H 2. n-BuLi (2 equiv.), TMEDA, EtzO, 25°C 3. R"-R" K ^

R 4.2M HCI, H2O R

^ 8 5 1 H2N NH2 , EtOH, reflux

2. Cu(0Ac〉2, MeOH, reflux

R" R"

1 R" = f-Bu; R 二 t-Bu 2 R" = f-Bu; R = SPh 3 R" = f-Bu; R = SPK 4 R" = t-Bu\ R = H 5 R" = H; R = SPh 6 R" = H ; R = H (Scheme 1 )

16

favourable to copper(II) ions. It is also believed that this distortion may enhance the

stability of the corresponding copper(I) species and facilitate the coordination of

alcoholate substrates to the copper center during the catalytic turnovers. The alkyl

substituents, R and R" at the ortho and para positions of the phenolate rings help to

stabilize the phenoxyl-radical species formed upon oxidation. It is noteworthy that

oxidation of complexes 1 and 2 gave thermally stable copper(II) phenoxyl-radical

species. These complexes can catalyze the oxidation of benzylic and allylic alcohols

to the corresponding aldehydes by molecular oxygen at room temperature with

turnover numbers in the range 30 to 1300 (Figure 7).

Chaudhuri, Wieghardt, and co-workers have reported two copper complexes (7

and 8) which showed reactivities similar to that of galactose oxidase, though the

coordination environment around the copper center in these complexes is far from

that of the native enzyme (Scheme In the solid state, compound 7 is a

monomer, whilst compound 8 is a dimer. The copper centers in both compounds

exhibit a distort square planar coordination geometry.

17

^ f ^ R = SPh, f-Bu t-Bu PhCHzO" latmO:

H2。V 'Bu \

PhCHjOH—

S i : p T ^ 器於 (-Bu t-Bu

Figure 7. Proposed mechanism of alcohol oxidation by complexes 1 and 2.

|-Bu |-Bu

air f-Bu-'^^S^^^f-Bu 0、c|u,0

-Bu -Bu j 、

f f ^ CuCI, EtgN 7 NBu- Y S MeCH’ Ar ⑷

OH OH f-Bu___ dry O2. THF ‘ [bu

L ^"Vbu 一 8

(Scheme 2)

18

Compounds 7 and 8 catalyze the oxidation of primary and secondary alcohols

to the corresponding aldehydes and glycol derivatives, respectively, together with

the concomitant conversion of dioxygen to hydrogen peroxide. Compound 8

catalyzes the oxidation of primary alcohols to aldehydes with a turnover number of

630. It has been shown that only one alcoholate substrate is bound to one of the

copper centers of the complex during the reaction (Figure 8). On the other hand,

both copper centers of 8 are bound by two alcoholate substrates during the catalytic

oxidation of primary alcohols. It is believed that the two alcoholate moieties bind in

a syn-fdiCidX way that C-C bond formation takes place between two coordinated ketyl

radical species.

2+ f-B^_ •““] 2+ > = < • RCH^OH

沾 u R / ^ H ^ ^ B u

H202-K '

o A

他 ~ I 2 + f - B ^ _ “ I 2+

H � � B U / 々絶

Figure 8. Proposed mechanism for the catalytic oxidation of primary alcohols by complex 8.

19

Cyclic voltammetry of 7 in dichloromethane shows two reversible one-electron

processes at £"1/2= -0.14 and —0.16 V (versus Fc+/Fc) while that of 8 shows two

reversible one-electron reduction waves at Ei/2== -1.26 and -0.29 V (versus Fc+/Fc).

Wieghardt and co-workers have also reported a series of copper(II) and zinc(II)

complexes derived from the macrocyclic ligands 9-14，which contain phenolate

pendants.6 Besides copper(II) phenolate compounds and their analogous zinc(II)

compounds have also been prepared in order to understand the chemistry of metal-

phenoxyl radical species. The reasons for studying the zinc(II) analogues are: (1)

zinc(II) ion is redox-innocent within a wide range of potentials, (2) the

corresponding phenoxyl radical species can be studied by EPR spectroscopy without

interference from paramagnetic metal centers, and (3) the electronic spectra of the

radical species are not affected by d-d transitions due to the metal center. As a

result, many research groups have studied both copper(II) and analogous zinc(II)

complexes as structural models for galactose oxidase.

T W Y Y h 3

11 1 2 R = t-Bu] R" = CH3

13 R = OCH3; R" = CH3

9 R = t-Bu 14 R = -Bu; R" = /-Pr 10 R = OCH3

20

Jean-Louis Pierre and co-workers have reported the dimeric copper complex

15, which was obtained by treating copper(II) perchlorate with the iV2<^2-type donor

ligand, bis(3 '-/-butyl-2 '-hydroxybenzyl)(2-pyridylmethyl)amine, and triethylamine

Q

at room temperature (Eq. 5). Complex 15 could be converted to the monomelic

complex 16 upon addition of acetonitrile (Eq. 5).

A

代一於 Z � - 3 f-Bd I r NBi! W 16

15 (Eq. 5)

Apart from these, the same research group also reported the mononuclear

copper complex 17，which could catalyze the oxidation of primary alcohols to

aldehydes with more than 30 turnovers in a basic medium.^ The electrochemical

feature of 17 in dimethylformamide was studied with cyclic voltammetry. Three

successive redox processes have been observed in the anodic region. The first one

was quasi-reversible with Em = 0.11 V and the other two appeared to be irreversible

with £pa = 0.45 and 0.76 V. However, the catalytic mechanism for the oxidation of

alcohols by this compound remains unclear.

21

t-Bu t-Bu

17

Tolman and co-workers have prepared a series of macrocyclic ligands 18-23,

containing isopropyl substituents, by modification of ligands 9-14 (Eq.6).^^

A CH30H ^ 人

令u令 + —q.) + - ^ Y 18 R = R' = CH3

19 R = R' = t-Bu 20 R = CH3； R = OCH3 21 R = CH3； R. = SCH3 22 R = /-Bu; R. = SCH3

H R OH _ _ OH

> + HCHO(aq.) + 2 O I J { > M

丫 U H • X ^ X 23

(Eq. 6)

Deprotonation of 18-23 with sodium hydride followed by treatment with

anhydrous metal salts [CuCl2, Cu(03SCF3)2，Cu(02CCH3)2’ and ZnCy in

tetrahydrofuran gave a series of monomelic metal-phenolate complexes. Copper(II)

22

and zinc(II) complexes derived from ligands 19 and 23 could be chemically oxidized

to give the corresponding metal-phenoxyl radicals by treatment with stoichiometric

amounts of either cerium ammonium nitrate in acetonitrile at -40°C or

thianthryljtetrafluoroborate in dichloromethane at -80 。C. Spectroscopic

characterization of these metal-phenolate complexes and the corresponding metal-

radical species have also been carried out. With ligand 19, the copper complex 24

has been prepared. ^ Treatment of 24 with NaOCHsPh gave the corresponding

copper benzyl alkoxide complex, which could be oxidized electrochemically to give

benzaldehyde, 1,4-di-isopropyl-1,4,7-triazacyclononane and 4，6-di-,孙 butyl-2-

formylphenol (Figure 9). These reaction products have been identified by ^NMR

and GC-MS analysis.

r n +

CP3SO3- N a O C H 2 P h 、〖 - B u ^ ^ ^ ^Q!^

24

CHO , D ？H electrochemical 人广 V V ^ " ^ * ^

• [1 I + \ / + 、IJ + unidentified Cu product(s) reaction ^ N ^ ^ 丫

~‘ 丁 t-Bu 46% < 5% < 5%

Figure 9. The catalytic reaction of complex 24.

23

Whittaker et al. have reported a dimeric copper(II) complex (25) by the

reaction of tetrakis(acetonitrile)copper(II) tetrafluoroborate with one equivalent of

the duncamine ligand and two equivalents of tetramethylammonium hydroxide.

Upon addition of pyridine, compound 25 could be converted to the monomeric

copper(II) species 26 (Eq. 1)}^

A y

丫 26 25 (Eq. 7)

A number of structural models for galactose oxidase have also been reported.

Fenton and co-workers have prepared a series of copper(II) complexes which

derived from the bispyridine ligands l l - Z l P Interestingly, the spectroscopic

features of the copper complexes were similar to those of the native enzyme,

although they did not show any catalytic behaviour.

24

/ = < N > = \ / = < N > = \

G n ( p h O G n ( / O H W

P P H O2N

27 X = y = 1 30 X = y = 1 28 X = y = 2 31 x = y = 2 29 X = 1; y = 2 32 x = 1; y = 2

By modification of ligand 28 with the incorporation of a thioether functionality

at the ortho position of the phenolate ring, Itoh and co-workers have reported a new

ligand 33.14

r y

k W Vbu t-Bu 33

Compound 33 reacted with copper(II) and zinc(II) salts to form the

corresponding metal complexes in which the metal centers have a five-coordinate

N3O environment. Although the coordination environment around the metal center

in these complexes are different from those observed in the native enzyme, both

metal complexes could oxidize benzyl alcohol to benzaldehyde upon chemical

25

oxidation with eerie ammonium nitrate. The involvement of a metal radical species

in the catalytic reaction cycles has been confirmed by resonance Raman

spectroscopy, electrospray ionization mass spectroscopy and EPR spectroscopy. It

was found that the oxidation of benzyl alcohol by the copper-phenolate complex

obeyed a first-order kinetics, whilst that of the zinc analog obeyed a second-order

kinetics. 14b

In this research work, with a modification of ligand 33 reported by Itoh and co-

workers, a series of N3O tetradentate ligands have been prepared. The preparation

of the ligands, the syntheses and structures of copper(II) and zinc(II) complexes, and

their characterization will be explained in the following sections.

26


2-B. Preparation of Tetradentate Ligands and Complexes

2-B-I. Preparation of A jO-type Tetradentate Ligands

A series of pyridine- and benzimidazole-based A(jO-type tetradentate proligands

34-39 (Scheme 3)，which contain substituted phenolate pendant, were used in our

studies.

n r ^ N, /口 " Y ^

V V R ' J T X ^ R R R

34 R = R '=f.Bu ( H L ” 3 7 R = R' = ^ B u (HL^)

35 R = f-Bu，R' = H (HL2 ) 38 R = f-Bu, R'= H (HL^ )

36 R = H,R = t -Bu (HL3 ) 39 R= H. R' = / -Bu (HL® ) (Scheme 3)

(a) Preparation of the Pyridine-based Proligands 34-36

The proligands 34-36 were prepared by reductive amination of substituted benzyl

bromides (46-48) with A^,A^-bis(2-pyridylmethyl)amine (BPMA) 49，in the presence

of tributylamine, in refluxing tetrahydrofliran (Scheme 4).

27

R n n 2. Et3N. r e f l u x ~ “ H O ^ ^ R .

46 R = R' = f-Bu R 47 R = f -Bu, R' = H 34 R = R' =t -Bu (HlJ) 84% 48 R = H, R' = f-Bu 35 R = f-Bu, R' = H (HL^) 80%

36 R = H.R' = f -Bu (hl3 ) 70% (Scheme 4)

The substituted benzyl bromides 46-48 were prepared from the corresponding

substituted phenols. Reaction of a refluxing solution of the appropriate substituted

phenols, tributylamine, tin(IV) chloride and paraformaldehyde gave the

corresponding benzaldehydes 40-42. Subsequent reduction of 40-42 with sodium

borohydride gave the respective benzyl alcohols 43-45. Bromination of 43-45 with

phosphorus tribromide led to the formation of a series of substituted benzyl bromides

46-48 in excellent yields (Scheme 5)7

f? f?

n-BuaN • (TS^OH

R ^ ^ -(CH20)n- R J 40 R = R-= f-Bu (80%) 41 R = f-Bu. R' = H(72%) 42 R = H, R' = NBu (70%)

睡 4 , 久 O H PBra，久 O H MeOH I ^ CHCI3 I J [ o,

43 R = R' = t -Bu (95%) 46 R = R' = f -Bu (95%) 44 R = f-Bu. R' = H (93%) 47 R = f-Bu. R '= H (96%) 45 R = H, R. = f -Bu (96%) 48 R = H, R_ = f -Bu (96%) (Scheme 5)

28

iV,iV-Bis(2-pyridylmethyl)amine 49 was prepared by treating a solution of 2-

pyridinecarboxaldehyde and 2-aminomethylpyridine, followed by reduction of the

resulting solution with sodium borohydride (Scheme 6).

f S + f S NaBH4， i T ^ ^ �N^"^NH2 + MeOH * S / ^ Y ^ ^ ^ N " ^ ^

H H 49 (90%) (Scheme 6)

(b) Preparation of the Benzimidazole-based Proligands 37-39

Reaction of iminodiacetic acid and o-phenylenediamine in refluxing methanol

gave 7V,A^-bis(2-benzimidazolymethyl)amine (BBA) 50 in 50% yield (Scheme 7).

^COOH H H

C ^ ^ N H U reflux ^ ^ ^ N ^ J ^ N " - ^

^COOH 刚 2 n SO ( 5 0 % ) (Scheme 7)

BBA 50 was prepared according to a modified procedure based on the one

reported by Stephan and co-workers/^ The reaction time has been shortened from

72 hours to 18 hours and the reaction yield has been improved from 28% to 50%.

29

The proligands 37-39 were prepared by an analogous procedure as for 34-36，by

treating BBA with the appropriate benzyl bromides 46-48 and triethylamine in

refluxing tetrahydrofliran (Scheme 8).

R O c V - J Y ^ ^ O H 1.5�’THF I … L Y ^ R "

R . J ^ ^ A / B r 2. EtsN, reflux H O ^ ^ R

46 R = R' = f -Bu 37R = R'=f-Bu (Hi / ) 51% 47 R = f -Bu, R' = H 3BR = t -Bu, R'= H (HL®) 40% 48 R = H, R' = f -Bu 39 R= H,R' = t -Bu (HL®) 36% (Scheme 8)

The crystal structure of galactose oxidase revealed that the equatorial tyrosinate

residue (Tyr 272) is linked to a nearby cysteine via an ortho C-S bond. However, an

S-alkyl substituent has not been introduced on the phenolate pendants of proligands

34-39 in order to avoid the formation of Cu-S b o n d s I n fact, bulky electron-

donating 〜butyl substituents have been introduced at the ortho and para postitions of

the phenolate moieties of 34-39 because (1) they help to stabilize the phenoxyl

radical species formed by electronic effect; (2) their bulkiness help to prevent

dimerization of the resulting copper complexes by a steric mean; (3) they help to

protect the phenoxyl radical species from attacks by other reagents in the

1 1 surroundings. These substituents exert different electronic and steric effects on the

30

ligands and hence their effects on the formation and properties of the resulting

complexes can be studied.

By comparing the structure of proligands 34-36 with that of 37-39, it should be

noteworthy that the latters provide a closer structural mimic to the histidine

coordination environment around the copper active site of the native enzyme. These

two series of ligands, with different steric and electronic properties, are expected to

exert different effects on the catalytic reactivities of the resulting complexes.

31

2-B-II. Preparation of Copper(II) and Zinc(II) Complexes

The copper(II) salts, Cu(C104)2.6H205b,6a’8’i8, Q i C O s S C F])]。， ,

Cu(BF4)2.H20i3b，i9 and CuCb^^''^^''^^ are common starting materials for the

preparation of model complexes of GAO. With the exception of CUCI2, these

copper(II) salts consists of weakly coordinating anions. Interestingly, some

copper(I) compounds, [Cu(NCCH3)4](C104)6c and CuCP'io，" may be used to prepare

copper(II) complexes by subsequent oxidation. For the preparation of zinc(II)

analogs, Zn(BF4)2 ^HsO^ Zn(C104)2 ^HsO^^ and ZnCl2^® are commonly employed.

In our research work, both CUCI2 and Cu(0Ac)2 have been used as starting

materials for the preparation of the copper(II) complexes. For the preparation of the

zinc(II) analogs, ZnCl� and Zn(0Ac)2 were employed. We reason that acetate is

present in the coordination sphere of the copper center of GAO in acidic media.

Accordingly, both Cu(0Ac)2 and Zn(0Ac)2 have been used as starting materials to

the corresponding metal complexes in our work, although reports on their use are

rare in the literatures.

The preparation of copper(II) complexes derived from proligands 34-39 have

been attempted. However, only copper(II) complexes supported by 34 have been

successfully prepared (Scheme 9). Although triethylamine is commonly used to

deprotonate phenol ligands, it is not basic enough to generate the phenolate ligands

32

in our studies. Thus, a strongly basic sodium hydroxide was used in our work.

Besides, the use of sodium hydroxide resulted in relatively clean reactions as the by-

products, sodium acetate and sodium chloride, precipitated out and could be readily

removed during work-up procedures.

一 t-Bu +

f - B u ^ Q _ X-

2. CuX2, CH3OH ^ = = < 7 T^N. ^

( X = C I . OAc) 力 \ X

S M ^ ^ ^ / N ^ ^ N 』 51 [CU(HL1)CI]CI (80%)

V V f - B u 52 [Cu(HlJ)(OAc)](OAc) (50%) HO-^W (-Bu f-Bu

34 HLI f - B u ^ Q 1.1.0MNaOH < C ^ � 飞 /

• z N � 2. CUX2, CH3OH Cu..

{X=CI, OAc ) C | Z

53 Cu(L1)CI (73%)

54 Cu(lJ)(OAc) (80%)

(Scheme 9)

33

Attempts to prepare copper(II) complexes supported by proligands 37-39 were

unsuccessful. Only an intractable oil was obtained after the reactions. Further

attempts to repeat the reactions in tetrahydrofliran with sodium hydroxide as a base

were also unsuccessful.

A series of zinc(II) complexes 55-59 with proligands 34-36 have been

successfully prepared using either triethylamine or sodium hydroxide as the base

(Scheme 10). The results are different from those observed for the copper(II)

analogs.

r i n ^ N ^ I ^ ^ N ^ I .E tgN or NaOH ^

V V R ' 2. ZnX2. CH3OH

( X = C I . OAc)

34 R = R'=t -Bu (HlJ) ^ ^

35 R = f -Bu, R' = H (HL2) 55 [Zn(L^)CI] (71%)

36 R = H’ R, = f -Bu (HL3) 56 [Zn(L2)CI] (56%)

57 [Zn(L^)CI] (51%)

58 [Zn(Li)(OAc)] (77%)

59 [Zn(L2)(0Ac)] (55%)

(Scheme 10)

34

Attempted preparation of zinc(II) complexes supported by proligands 37-39

were not successfully. Attempts to modify the reaction conditions such as

temperature, solvents and the bases used were unsuccessful and no isolabe products

could be obtained.

Details of the preparation of complexes are described in the Experimental

Section. For paramagnetic copper(II) model complexes prepared in our work, their

molecular structures could only be determined by X-ray crystallography. For y

diamagnetic zinc(II) analogs, their structures have been characterized by NMR

spectroscopy, in addition to X-ray crystallographic analysis.

Besides, the generation and characterization of radical species have also been

carried out. Details of the experimental procedures are described in the following

sections.

35

2-C. Characterization

2-C-L Structural Studies

The molecular structures of the copper(II) phenoxyl complexes [Cu(HL")X]X

(51，52) (n = 1, 2, 3; X = CI, OAc), as well as copper(II) and zinc(II) phenolate

complexes [M(L")X] (54-59) (M = Cu, Zn; « = 1, 2, 3; X = CI, OAc) have been

characterized by X-ray crystallographic analyses. A l l of the metal complexes exhibit

a distorted square pyramidal coordination geometry on the metal centers (Figures 10-

16). The structure of these complexes is similar to that observed for the active site of

the native enzyme. ( Selected bond distances and angles for these metal complexes

are shown in Tables 2-9. The Cu-0(phenol) bond distances (2.437-2.450 A ) of the

copper(II) phenoxyl complexes 51 and 52 are similar to the observed Cu-0(Tyr 495)

bond distance (2.69 A ) for the native enzymes, although the phenoxyl protons are not

deprotonated in our current complexes. Upon deprotonation of the phenolate

pendant，the Cu-0 (phenolate) distances are comparatively shorter. For the

copper(II) phenolate complex 54，only the Cu-N bond distances (2.040-2.289 A ) are

comparable to the corresponding distances observed for the native enzyme」

36

Q C ( 2 6 )

� 9 ) J i l i l ^ / ^ C(IO) I

C(15) C(14) \\ c m )爆

Figure 10. Molecular structure of [Cu(HL^)Cl]Cl (51) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 2. Selected bond distances (A) and angles (。）for [Cu(HL^)Cl]Cl (51).*

Cul-01 2.450 Cul-N3 1.990(5)

Cul-Nl 2.047(4) Cul-Cll 2.251(1)

Cul-N2 1.994(5)

01-Cul-Nl 89.0 N2-Cul-Nl 83.4(1)

01-Cul-N2 94.0 N3-Cul-Cll 96.7(1)

01-Cul-N3 93.2 N2-CUL-CLL 96.9(1)

N3-Cu1-N2 164.0(1) Nl-Cul-Cl l 176.0(1)

N 3 - C U 1 - N 1 8 2 . 6 ( 1 ) 01-Cul-Cll 9 4 . 9

The numbers in parentheses are the estimated standard deviations in the last digit.

37

C(26)

c(27)

C ( 2 4 , ( ^ ^ C , 2 5 ) c(29)

CO)

Figure 11. Molecular structure of [Cu(HL^)(OAc)](OAc) (52) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 3. Selected bond distances ( A ) and angles (°) for [Cu(HL^)(OAc)](OAc) (52)广

Cul-01 2.437(7) Cul-N2 2.006(8)

Cul-02 1.905(7) Cul-N3 2.044(7)

Cul-Nl 1.989(8)

01-Cul-Nl 91.1(3) 02-Cul-Nl 98.5(3)

01-Cul-N2 92.8(3) 02-Cul-N2 96.7(4)

01-Cul-N3 88.0(3) 02-Cul-N3 173.8(3)

Nl-Cul-N2 164.5(4) Nl-Cul-N3 81.5(4)

01-Cul-02 85.7(3) N2-Cul-N3 83.6(4)


38

O C ( 2 1 )

V 2 0 ^ C ( 2 3 )

cn4) J

I yaiG) N(3) J 0(1)/ C(4) YC(24)

I � ^ ^ > 0 ( 2 1 A I 0(3) O:(28) CdO) Cl J j \ y C(ll) C(29) Figure 12. Molecular structure of [ C U ( L ' ) ( O A C ) ] (54) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 4 . Selected bond distances (A) and angles (。）for [C U ( L ' ) ( O A C ) ] ( 5 4 ) . '

Cul-01 1.942(2) Cul-N2 2.040(2)

Cul-02 1.969(1) Cul-N3 2.078(2)

Cul-Nl 2.289(3)

01-Cul-02 92.11(8) Ol-Cul-Nl 98.20(9)

01-Cul-N2 156.46(9) 02-Cul-Nl 98.03(9)

02-Cul-N2 94.24(9) N2-Cul-Nl 103.3(1)

02-Cul-N3 174.19(9) N2-Cul-N3 80.53(9)

01-Cul-N3 93.69(9) N3-Cul-Nl 80.84(9)

The numbers in parentheses are the est imated standard deviat ions in the last digit.

39

OC(251 广 1)

I C(22) /

C(23)

VI C )C (13 )

C(3) C(4) ⑶

C(11)

Figure 13. Molecular structure of [Zn(L^)Cl] (55) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 5. Selected bond distances ( A ) and angles (。）for [Zn(L^)Cl] (55)广

Znl -01 1.920(1) Znl-N2 2.134(2)

Znl -Cl l 2.294(1) Znl-N3 2.269⑵

Zn l -N l 2.078(2)

01-Znl-Nl 105.30(8) 01-Znl-Cl l 101.93(6)

01-Znl-N2 128.38(9) N l -Zn l -C l l 99.08(7)

Nl-Znl-N2 119.12(9) N2-Znl-Cl l 95.98(7)

01-Znl-N3 91.22(7) N2-Znl-N3 75.09(8)

Nl-Znl-N3 77.61(8) N3-Znl-Cl l 166.84(5)

• The numbers in parentheses are the estimated standard deviations in the last digit.

40

O C ( 2 1 )

C(17) I

l l b y ^ C(22) C c { 2 3 )

\ o ( 1 )

CO) a .

C(IO)


Table 6. Selected bond distances (A) and angles (。）for [Zn(L^)Cl] (56). '

Z N L - 0 1 1.934(2) Zn l -N2 2.107(3)

Znl-Cll 2.321(1) Znl-N3 2.298(3) Znl-NM 2.134(3)

0 1 - Z n l - N l 125.20(1) O l - Z n l - C l l 99.97(8)

0 1 - Z n l - N 2 113.1(1) Nl -ZnI-CI l 98.71(8) Nl-Znl-N：! 113.8(1) N2-Znl-Cll 99.32(9)

N l - Z n l - N 3 75.4(1) N2-Znl-N3 77.0(1)

O l - Z n l - N 3 89.4(1) N3-ZnI-CIl 170.66(7) • The numbers in parentheses are the es t imated standard devia t ions in the last digit.

41

C ( 9 ) O Q C ( 1 0 )

I Vi”）

\ 1 C(13)

有 / 。"‘ Cld)


Table 7. Selected bond distances ( A ) and angles (。）for [Zn(L^)Cl] (57).*

Znl-01 1.926(2) Znl-N2 2.104(2)

Znl-Cl l 2.3209(8) Znl-N3 2.269(2)

Znl -Nl 2.116(3)

01-Znl-Nl 116.9(1) 01-Znl-Cll 98.24(6)

01-Znl-N2 124.60(9) Nl -Znl -Cl l 100.54(8)

Nl-Znl-N2 112.5(1) N2-Znl-Cll 96.07(7)

Nl-Znl-N3 76.2(1) N2-Znl-N3 77.65(9)

01-Znl-N3 90.80(8) N3-Znl-Cll 170.89(6)


42

C(21) C(22)

尸 C ( 2 3 )

J k m y P c(26)

Njh^f^⑶ 5)

0(3)令 (2) C ( ^ c n i )

V C ( 2 8 )

O c ( 2 9 )

Figure 16. Molecular structure of [Zn(L^)(OAc)] (58) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 8. Selected bond distances ( A ) and angles (°) for [Zn(L^)(OAc)] (58)广

Znl-01 1.936(1) Znl-N2 2.127(1)

Znl-02 2.016(1) Znl-N3 2.236(1)

Znl-Nl 2.080(1)

01-Znl-Nl 112.85(6) Ol-Znl-02 106.10(6)

01 -Zn 1-N2 119.61(6) Nl-Znl-02 97.53(7)

Nl-Znl-N2 121.86(6) N2-Znl-02 90.80(6)

Nl-Znl -N3 77.79(7) N2-Zn 1-N3 76.73(6)

01-Znl-N3 92.50(6) N3-Znl-02 161.09(6)


43

； ; ^ I C ( 1 2 ) ^ ©CdO)

^^^ r .

Figure 17. Molecular structure of [Zn(L^)(OAc)] (59) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 9. Selected bond distances ( A ) and angles (。）for [Zn(L^)(OAc)] (59).*

Znl-01 1.997(1) Znl-N2 2.122(2)

Znl-03 1.939⑴ Znl-N3 2.239(1)

Znl-Nl 2.088(2)

01-Znl-Nl 97.38(8) O l - Z n l - 0 3 106.45(7)

01-Znl-N2 90.18(8) N l - Z n l - 0 3 114.08(8)

01-Znl-N3 160.87(8) N 2 - Z N L - 0 3 119.21(7)

Nl-Znl-N2 121.19(8) Nl-Znl-N3 78.11(8)

N2-Znl-N3 76.82(8) N3-Znl-03 92.24(7)


44

2-C-II. Spectroscopic Studies

In this work, four copper(II) complexes, 51-54，were structurally characterized

by X-ray crystallography and elemental analyses. Copper(II) and zinc(II) phenolate

complexes derived from HL^ (34) were further studied and characterized in order to

correlate their solution structures with that of the solid state, and to understand the

electronic influences of the phenolate substituents.

The X-band electron paramagnetic resonance (EPR) spectra of all copper(II)

complexes of N3O ligands (51，52，53，54) taken at 77K exhibited axial signals with

g//-values in the range of 2.26 and 2.28 and g丄-values within 2.04 and 2.08. The

signals for copper(II) complexes are consistent with those of the reduced inactive

form of the native enzymes (g" = 2.28 and g丄=2.05).^ A l l zinc(II) complexes were

EPR silent.

The UV-Vis spectra of all zinc(II) complexes did not show any absorption band

within the range of 350 nm to 1100 nm. For the copper(II) acetate complex 54，a

sharp absorption band at 492nm was observed at room temperature which is assigned

to the PhO -»Cu(II) ligand-to-metal charge transfer (LMCT) transition.

Consequently, the complex acquires a deep blue coloration.⑴�

Al l complexes have been characterized by mass spectrometry. Their LSI or EI

mass spectra showed the corresponding isotopic ion distribution of [M]+ species

45

(Figures 18-22). However no parent peak signals have been observed in the LSI

mass spectra of the acetate complexes 54 and 58.

The 1h and ^ C NMR spectra of the N3O ligands 34-39 and the zinc(II)

complexes 55-59 have been measured. Upon complexation, the two methylene

protons located next to the pyridine ring are shown to be chemically non-equivalent.

They coupled to each other to give two doublet signals. For example, for complex

55，the two doublets appeared at (54.05 and 4.14 (Figure 23), while for complex 58，

they were resolved at (54.19 and 4.26 (Figure 24)。

46

P o s i t i i o n L — S I M S S p e c t r u r r x o i ' E C ： A O a , i . ( u s i n s N B A a ， m a t r i x )

.r, r- -f ：二

二汁 I . ： - J r •二. I • V ... ；.>0 r-- �� 4000000 - ro 寸 uOLOf COCl - LT) LT) LO ltj u un LD

3 0 0 0 0 0 0 二

5 I 2 0 0 0 0 0 0 -

： , i j 1000000 - j j

,： juJvjLILLL ‘ I ‘ ‘ I ‘ ‘ ‘ ‘ 1 ‘ ‘ ‘ ‘ 1 1 1 ‘ ‘ 1 1 1 1 1 1~

50S 511 51S 521 52S m/z

Figure 18. The LSI mass spectrum of [Cu(HL^)Cl]Cl (51).

； f t ^ ^ r ^ l S 。 = l L " E n c t 〜 m Of ECA03：

4.Oe+07 一 T-.l 吁 r 产.

U.: ("O ^ ’一

3 . 5 e + 0 7 - — 一一 — —

_ ‘ - lo CO r-w CO cr> - U-) LO to LT) LO

3 . 0 e - f 0 7 一

2.5e+07 一：“ I

2 . O e + 0 7 —; |j ] I 1 . 5 e > 0 7 —

1 . O e + 0 7 - I I

: 丨 I ： I I 1

5.0e-06 - I I ! !

。、。。： ^jjujUiJLj一 -5 .Qe+Q6 - ^ r~---r-

5 0 9 5 1 4 ‘ ‘ ‘ ‘ ~ _‘ ‘

二丄3 5 2 4 5 2 9 m / z

Figure 19. The LSI mass spectrum of [Cu(L^)Cl] (53).

47

S E u n d i n c a “ ~ A v e r a g e of 9.845 Co 9.94S tnin.： E C A 0 3 3 . D 240000 ^ 3 l 2

1 9 6

220000 -

200000 -

180000-

I S O O O O -

1 4 0 0 0 0 -

1 2 0 0 0 0 -

100000 - 幻

8 0 0 0 0 -

S O O O O - 1 119 198

40000- I … 58 40 7 425 20000. I 133 I J 219 267 306

0 • , , J l M . t t f i . , 1 , 1 . 1 , ,，,.I|Im, , J | I . , 〒 f , 、 , I „ i , l l , , 1 , 1 . ？357 3 7 9 … ! J 丨

n/z--> 40 S O a o 1 0 0 1 2 0 1 4 0 1 6 0 l a o 200 2 2 0 2 4 0 2 S 0 2 8 0 300 3 2 0 3 4 0 3 6 0 3 8 0 4 0 0 4 2 0

Figure 20. The EI mass spectrum of [Cu(L^)(OAc)] (54).

a.i. ” Po s'ltive ion L —SiMS Speo trtam of ECA03S ,\.siTis NBA as matrix ) 2 .0e+.07

“ �uo oo 寸 CT) LO r- • uo csi CO o r CO CO . " OD f CO to �� 1.5e+07 — uo '-JD r CO CD CO

‘ 一一一 _ _ C s l C ^ J 1 un Ln un LO Ln Ln un ；观 V

1.0e-f07 -“

5.0e+06 - I I

: ， I ！ || I - i /働 ill , l| 0.0e.00 ‘ .—LU丄丄、�> a.丨wL«�ij丄L

‘ —I ‘ I ””‘ '1 r一—— r — ‘ - I — , r. •一 480 500 520 m/z

Figure 21. The LSI mass spectrum of [Zn(L^)Cl] (55).

48

a.i. - --'o. -：. li-^e i o n L … . S I U S S p e c： Lr 1.1 m o f E C A O S o (•-••si x ^ N B A a s m a t r i x )

:： S.0e>03,

“ : : - T ： rj-)

•• r-v ‘ ― • — 一

_ 00 oc c o c o - T -sr

6.0e>08 - ^ ： ^ “

S.Oe+03 -

4.0e+08 -

3.0e-^08 - 、.

2.0e+08 -

1.0e-f08 -

- ^ ^ _ _ _ _ _ _ O.Oe^OO ^ • ‘ •'"' —

1 ‘ • ‘ 1 ‘ ^‘ • • _•-， 1 ‘ ‘~ 490 540 590 m/z

Figure 22(a). The LSI mass spectrum of [Zn(L^)(OAc)] (58).

A b u n d a n c e A v e r a g e o t S . 1 2 2 Co 5 . 5 7 9 m i n .： E C A O S S . D .

9(3

4 0 0 0 0 - 3 1 9

3 5 0 0 0 -

261 425 3 0 0 0 0 -

58 4 3 2

2 5 0 0 0 -

2 0 0 0 0 - 1 9 8 3 8 6

119 丨！|

I S O O O . 5 4 0

10_- , 232

。.J此 iiiiliLi iij J灿 k iiux 丄 ^ njUi 50 1 5 0 2 0 0 ^ ^ ^ ^ ^ 55o'‘

Figure 22(b). The EI mass spectrum of [Zn(L^)(OAc)] (58).

49

S

M K

P

I

•

.

丨

L

咖

饥 g

•

肌

iiti F工

f.^^

一…『L二

I

」：i

sm c-snsrs讯ssrssgss^s

！狀sSS

sa⑴q…i

Jo

lo

j il

5

『

^

Sri MMMMMMMMMMMMMMMMMMM

f—^

Ao^

a

1

-—_

KM^I^ ⑶

；”；= I

MMMM^ffi

) 认

-2

1

o

^ ——

maim

,2

X

,

J i

I-寬

L

:

L斤 ^

—-^Affl

棚

【【、

ul—

o

二『c

Myui

i ^

s

l^nl

m

p ！4

V

J

ylu

-g

o

. ,5

嫩 K

fl^

印

！一『厂 ^

i

J ,6

H

i.么 nl

7

3.

1

vi

^

: p

”；〒

s

遣丄I

3

i等

丄I

3

I

M

‘ I_

H

s- m Jy l\

.9

—9

A5S

~ 699,0、

ia

.

w n

；i!

^^

maa

li

2-D. Generation of Metal Phenoxyl Radical Species

Metal-radical array plays a very important role in many metalloproteins and

on

catalytic reactions.

Copper(II) and zinc(II) phenolate complexes (53, 54，58，59) could be oxidized

with one equivalent of eerie ammonium nitrate (CAN) in dry dichloromethane under

nitrogen at -80 °C to generate the corresponding metal phenoxyl radical species

(Scheme 11).

R, ^ J ^ '

^ ^ (剛C e > 0 3 ) 6 ] i CH2CI2 -80 °C y

0 亡

M = Cu, Zn X = CI, OAc

R = f-Bu; R' = t-Bu, H (1_1’2) R=H,. R' = t-Bu (l3) (Scheme 11)

Upon oxidation with CAN at -80。C，the solutions acquired a deep green

coloration immediately. The deep green intermediate species were stable only at low

temperatures (<-40 °C). However, for the copper(II) phenoxyl complex (51)，no such

51

observable change was observed upon oxidation. Both EPR and UV-vis

spectroscopy were used to characterize the intermediate species in our work.

No obvious change has been observed in the EPR spectra of compound 51 both

before and after oxidation with CAN (Figure 25), suggesting that the compound was

inert toward oxidation and no evidence for the existence of any radical species has

been observed. On the other hand, both complexes 53 and 54 exhibited typical axial

Cu(II) signals before oxidation. Upon oxidation with CAN at -80 °C, the signal

amplitudes diminished substantially (Figures 26 and 27). These suggest the

formation of Cu(II) phenoxyl radical species. However, evidence on whether the

phenoxyl radical is tightly or loosely bound to the copper center is still missing in

these cases. Oxidation of the zinc(II) complex 58 gave a nearly isotropic signal at g

=2.00 (Figure 28)，indicating the existence of the corresponding phenoxyl radical

species.

Further evidences on the existence of the radical intermediates could be

obtained from UV-Vis spectroscopy. Only complexes 54 and 58 were fully

characterized. The absorption band for the former complex 54 shifts from 491 nm to

413 nm and 662 nm upon oxidation with CAN (Figure 29). No absorption feature

has been observed in the range from 350-1050 nm for 58. Upon oxidation with

52

CAN, two absorption maxima at 406 nm and 753 nm were observed (Figure 30).

These absorption features suggest the existence o f phenoxyl radical species.^' ^

On the basis o f EPR and UV-vis spectroscopy，highly reactive phenoxyl radical

species have been successMly generated by chemical oxidation o f metal phenolate

complexes with C A N at very low temperatures.

& ^ “ I ——51 +CAN

2400 2600 2800 3000 3200 3400 3600 3800 4000 Magnetic Field (Gauss)

Figure 25. EPR spectra of [Cu(HL^)Cl]Cl (51) at 77K. Instrumental parameters: microwave power，0.2 microwatts; microwave frequency, 9.443 GHz; modulation amplitude, 2 G; modulation frequency, 100 kHz.

53

g// = 2.26 g丄=2.081 —53

—53 +CAN

_ _ _ _ _

, H I a / / -144.5 G \ ^ a丄=42.9 G ^

1/

2400 2600 2800 3000 3200 3400 3600 3800 4000

Magnetic Field (Gauss)

Figure 26. EPR spectra of [Cu(L^)Cl] (53) at 77K. Instrumental parameters: microwave power, 0.2 microwatts; microwave frequency, 9.438 GHz; modulation amplitude, 6 G; modulation frequency, 100 kHz.

I —

g 丄 = 2 . 0 4 — 5 4

g// = 2.27 —54 +CAN

^ J I a//= 141.7 G

a 丄二 26.9 G

2400 2600 2800 3000 3200 3400 3600 3800 4000

Magnetic Field (Gauss) Figure 27. EPR spectra of [Gu(L^)OAc] (54) at 77K. Instrumental parameters: microwave power, 0.1 microwatts; microwave frequency, 9.443 GHz; modulation amplitude, 5 G; modulation frequency, 100 kHz.

54

—58 + CAN

宅 J ‘

^ I

2800 3000 3200 3400 3600 3800 4000

Magnetic Field (Gauss)

Figure 28. EPR spectrum of [Zn(Li)(OAc)] (58) at 77K. Instrumental parameters: microwave power, 0.2 microwatts; microwave frequency，9.438 GHz; modulation amplitude, 2 G; modulation frequency, 100 kHz.

3 r ——n ——54

2.5 ——54 + C A N

0 350 450 550 650 750 850 950 1050

wavelength (nm)

Figure 29. UV-vis spectra of [Cu(L^)(OAc)] (54) at room temperature.

55

0.7 [― 〒

— 5 8 0.6

— 5 8 + C A N 0.5

S 0.4 \f\ s 召 0.3 o

# 0.2 \

0.1 V “ 0 ^ “ — ~ —

-0.1

350 450 550 650 750 850 950 1050

wavelength (nm)

Figure 30. UV-vis spectra of [Zn(L^)(OAc)] (58) at room temperature.

56

2-E. Summary

In conclusion, a series of mononuclear copper(II) and zinc(II) complexes (51-

59) with tripodal tetradentate A/jO-type ligands were successfully synthesized as

mimics to the active site of galactose oxidase. X-Ray crystallography revealed a

distorted square pyramidal N3O coordination sphere around the metal center in these

complexes. Thus, these complexes serve as structural models for the reduced

inactive form of the active site of GAO. On the basis of EPR and UV-vis

spectroscopy, highly reactive phenoxyl radical species were successfiilly generated

by chemical oxidation of the corresponding metal phenolate complexes with cerium

ammonium nitrate.

The oxidation of primary alcohols to the corresponding aldehydes catalyzed by

these complexes have also been investigated. Unfortunately, none of the complexes

reported in this work showed catalytic properties towards oxidation of alcohols to

aldehydes. During optimization of the reaction conditions for this catalysis,

Yamauchi and co-workers have reported a series of copper(II) and zinc(II)

complexes and two of them were prepared by ligand HL^ (34) used in our studies. ^

However, the difference between our complexes (53-55, 58) and those complexes

reported by the Japanese research group is on the choice of counter anions. They

used mixed counter anions, CIO4" and CI" for the preparation of copper(II) complex,

57

but C r for the preparation of the zinc(II) complex supported by l A Besides, similar

approaches have been employed by both research group in the studies of the

phenoxyl radical species.

By using ligands 34-39, several copper(I) complexes were synthesized and their

chemistry has been found to be totally different from that of their copper(II)

counterparts, as wil l be described in Chapter 3.

58

2-F. References

1. Ito, N.; Philips, S. E. V.; Stevens, C.; Ogel, Z. B.; McPherson, M. J.; Keen, J. N.;

Yagaz, K. D. S.; Knowles, P. F. Nature 1991，350, 87-90.

2. Whittaker, M. M.; Whittaker, J. W. J. Biol Chem. 1988, 262, 6074-6080.

3. Whittaker, M. M.; Ballou, D. P.; Whittaker, J. W. Biochemistry 1998，37, 8426-

8436.

4. (a) Wang, Y.; Stack, T. D. P. J. Am, Chem. Soc. 1996, 13097-13098; (b) Wang,

Y.; BuBois, J. L.; Hedman, B.; Hodgson, K. O.; Stack, T. D. P. Science 1998，

279, 537-540.

5. (a) Chaudhuri, P.; Hess, M.; Florke, U.; Wieghardt, K. Angew. Chem. Int. Ed.

1998，37, 2217-2220; (b) Chaudhuri, P.; Hess, M.; Muller, J.; Hildenbrand, K.;

Bill, E.; Weyhermuller, T.; Wieghardt, K. J. Am. Chem. Soc. 1999，121, 9599-

9610.

6. (a) Sokolowski，A.; Lentbecher, H.; Weyhermuller, T.; Schnepf，R.; Bothe, E•；

Bill, E.; Hildebrandt, P.; Wieghardt, K. J. Biol Chem. 1997’ 2’ 444-453; (b)

Schnepf, R.; Sokolowski, A.; Muller, J.; Bachler, V.; Wieghardt, K.;

Hildebrandt, P. J. Am. Chem. Soc, 1998, 120, 2352-2364; (c) Muller, J.;

Weyhermuller, T.; Bill, E•； Hildebrandt, P.; Ould-Moussa, L.; Glaser, T.;

59

Wieghardt, K. Angew. Chem. Int. Ed. 1998，57, 616-619; (d) Bill, E.; Muller, J.;

Weyhermuller, T.; Wieghardt, K. Inorg. Chem. 1999, 38, 5795-5802.

7. Sokolowski, A.; Muller, J.; Weyhermuller, T.; Schnepf，R.; Hildebrandt P.;

Hildenbrand, K.; Bothe, E.; Wieghardt, K. J. Am. Chem. Soc. 1997，119, 8889-

8900.

8. Zurita, D.; Gautier-Luneau, L; Menage, S.; Pierre, J. L.; Saint-Aman, E. J. Biol.

Inorg. Chem. 1997, 2, 46-55.

9. Saint-Aman, E.; Menage, S.; Pierre, J. L.; Defrancq, E.; Gellon, G. New J .

Chem. 1998，393-394.

10. Halfen, J. A.; Jazadzewski, B. A.; Maphapatra, S.; Berreau, L. M.; Wilkinson, E.

C.; Que, L., Jr.; Tolman, W. B. J. Am. Chem. Soc. 1997，119, 8217-8227.

11. Halfen, J. A.; Young, V. G.，Jr.; Tolman, W. B. Angew. Chem. Int. Ed. Engl

1996, 55, 1687-1690.

12. Whittaker, M. M.; Duncan, W. R.; Whittaker, J. W. Inorg. Chem. 1996，35’ 382-

386.

13. (a) Adams, H•； Bailey, N. A.; Rodriguez de Barbarin, C. O.; Fenton, D. E.; He,

Q. Y. J. Chem. Soc” Dalton Trans. 1995, 2323-2331; (b) Adams, H.; Bailey, N.

A.; Campbell, I. K.; Fenton, D. E.; He, Q. Y. J. Chem. Soc., Dalton Trans. 1996,

2233-2237.

60

14. (a) Itoh, S.; Takayama, S.; Arakawa, R.; Furuta, A.; Komatsu, M.; Ishida, A.;

Takamuku, S.; Fukuzumi, S. Inorg. Chem. 1997，36, 1407-1416; (b) Itoh, S.;

Taki, M.; Takayama, S.; Nagatomo, S.; Kitagawa, T.; Sakurada, N.; Arakawa,

R.; Fukuzumi, S. Angew. Chem. Int. Ed. 1998，38, 2774-2776; (c) Itoh, S.; Taki,

M.; Kumei, H.; Takayama, S.; Nagatomo, S.; Kitagawa, T.; Sakurada, N.;

Arakawa, R.; Fukuzumi, S. Inorg. Chem. 2000, 39, 3708-3711.

15. Berends, H. P.; Stephan, D. W. Inorg. Chim. Acta 1984，93’ 173-178.

16. Whittaker, M. M.; Chuang, Y .Y.; Whittaker, J. W. J. Am. Chem. Soc. 1993，

115, 10029-10035.

17. Chaudhuri, P.; Hess, M.; Weyhermuller, T.; Wieghardt, K. Angew. Chem. Int.

Ed. 1999, 38, 1095-1098.

18. Shimazaki, Y.; Huth, S.; Odani, A.; Yamauchi, O. Angew. Chem. Int. Ed. 2000，

39, 1666-1669.

19. Halcrow, M. A.; Chia, L. M. L.; Liu, X.; Mclnnes, E. J. L.; Yellowlees, L. J.;

Mabbs, F. E:; Scowen, 1. J.; McPartlin, M.; Davies，J. E. J. Chem. Soc., Dalton

Trans., 1999，1753-1762.

20. Stubbe, J.; Donk, W. A. Chem. Rev. 1998，98, 705-762.

21. Shimazaki, Y.; Huth, S.; Hirota, S.; Yamauchi, O. Bull Chem. Soc. Jpn. 2000,

75,1187-1195.

61

CHAPTER 3

Copper(I) Complexes with N3O Tetradentate Ligands

3-A. Introduction

3-A-I. Studies on copper(I) complexes with oxygenation

Oxidation reactions play a very important role in various biological and

industrial processes. The use of dioxygen as the primary oxidant has attracted much

interest in the chemical industry.【Copper plays a crucial role in proteins involved in

electron transfer and dioxygen processing (Table 10). Besides, it has widespread

applications in both stoichiometric and catalytic oxidative transformation. The

interaction between copper(I) and dioxygen is a key component for both chemical

and biological processes. Thus, much interest has been attracted to the investigation

on the binding, interaction, and subsequent reactivity of dioxygen with copper ion

centers.

A number of dioxygen binding modes in copper complexes have been

^ 1

proposed. Figure 31 shows the six common ligation modes: end-on, r) -superoxo,

side-on, ri^-superoxo, |a-l,2-peroxo, |a-Ti :ri -peroxo, bis-)i-oxo and |i-hydroperoxo.

62

Table 10. Copper proteins involved in dioxygen processing.

Protein Biological Function Oxygen Carrier Hemocyanin* O2 transport

Copper Monooxygenases Tyrosinase tyrosine oxidation Dopamine p-monooxygenase (DpM) dopamine->norepinephrine Peptidylglycine a-amidating monooxygenase (PAM)* oxidative N-dealkylation Methane monooxygenase (MMO) methane—methanol Ammonia monooxygenase (AMO) ammonia->hydroxylamine Copper Dioxygenases Quercetinase quercetin oxidative cleavage

Copper Oxidases 'Blue，multi-copper oxidases (converting O2 to 2H2O) Laccase* phenol and diamine

oxidation Ascorbate oxidase* oxidation of L-ascorbate Ceruloplasmin* Fe(II)->Fe(III) and/or radical

scavenging

'Non-blue ‘ oxidases (converting O2 to 2H2O2) Amine oxidase* elastin, collagen formation

and alcohol oxidative deamination

Galactose oxidase* galactose oxidation alcohol—aldehyde

Glyoxal oxidase aldehyde->carboxylic acid Phenoxazinone synthase phenoxazinone formation

and oxidative coupling

Heme-copper oxidases terminal oxidases Cytochrome c oxidase (CcO)* proton translocation (pump) Quinol oxidase

Others Superoxide dismutase (SOD)* O2' dismutation

(detoxification) *X-ray structure(s) available.

63

- -11+ 1+ 「 -|2+

c u - \ H < 1 CU.....O _ _ L J 〇、-CLi

厂 l2+ r ^2+ ^ O� 「 J 1 +

广. . . -0- . . . / \ C u . 、 . , C u

Cu:、、人...-Cu Cu； :Cu 、〇••

O H - -I L J 匕 J

Figure 31. Dioxygen binding modes in copper complexes.

Most of the copper proteins in Table 10 have been introduced in Chapter 1. The

following section gives a brief review on the chemistry of copper complexes with

oxygen binding modes.

3-A-II. Studies on copper complexes with oxygen binding

Although copper-dioxygen complexes are important in many catalytic oxidation

reactions, only a few of the corresponding intermediates in these reactions have been

characterized, and the structural factors substantiating the catalytic effectiveness of

the copper complexes remain unclear. The reasons for the development of the

oxidation chemistry of copper-dioxygen complexes are: (1) providing the basis for

designing and developing new catalysts, and (2) being found to be common in highly

efficient biooxidation.

64

It has been suggested that copper-hydroperoxo species (Cu„-OOH; n = 1, 2) are

intermediates in many enzymatic reactions. These species have been known to be

key intermediates in the catalytic reactions of dopamine p-monooxygenase and

peptidylglycine a-hydroxylating monooxygenase. It was also proposed that these

species involve in the disproportionation of superoxide catalyzed by copper-zinc

superoxide dismutase (SOD), and the reduction of dioxygen to water by laccase and

multicopper oxidases.

Sorrell and co-workers have reported the dioxygen reactivities of dinuclear

copper-phenolate and -phenol complexes (60-64) with pyrazole and pyridine donors

(Schemes 12-14).4 In their reaction with dioxygen, the corresponding peroxo and

hydroperoxo adducts were generated at low temperature (Scheme 15).4

R

b ' " ' J n C I 八 — ^ 力〜叫 _ _ .

. a 亏 C I . Q Q . 乂严、 t h f 1 y ^ ^ ^ H

60 R = H

61 r = ch3 (Scheme 12)

65

p a y

62 (Scheme 13)

thf ,

63 R = H

64 r = ch3 (Scheme 14)

Dinucleating ligands 60 and 61 are unsymmetrical, whilst the 62-64 are

symmetrical. In these ligands, the para methyl substituent of the phenol group

prevents further substitution during the reactions. At -78 °C，the copper(I) phenolate

species 65，which showed no absorption in the UV-Vis region, reacted rapidly with

dioxygen to yield the copper(II)-peroxo adduct 70 (2:1 Cii:02)，which was

characterized by an intense absorption at about 500 nm (a peroxide to Cu(II) charge-

transfer band), a smaller band at about 395 nm (a phenoxide to Cu(II) charge-transfer

band), and a shoulder at about 630 nm (a peroxide to Cu(II) charge-transfer band).

66

r 「 a T 彻会。..

y y 一 J 一

65 1.0H- Z 66 “ \s^CU(ch3CN)4+

/ P、

OH- d^X^ 丄。"

Cu(CH3CN)4>/ J \CU(CH3CN)/

60-64 P = Py, Pz, DMP P" = Py, Pz, DMP 2+

一 P P \ p CO p p p u C u Q p C u OC-CuCQ

乙 p " , -CO

y y 67 68

02 CH2CI2 -78。C

1 f PPha 0=PPh3

- H? n2+ \ f

举 : X X \ + H+, 25。C

- 丫 -69 -78°C\ . 「 "] +

65 " " " " P , ^ ； ^ 込 ” -78。C I L ^

70

where DMP = 3,5-dimethyl-l-pyrazole (Scheme 15)

67

The copper(I) phenol species 67 and 68 also reacted with dioxygen at very low

temperature to form a // -OOH copper(II) species, which were characterized by an

intense absorption at about 395 nm in the UV-Vis region. This species gave

triphenylphosphine oxide and the corresponding i i -hydroxo- j i -phenoxo copper(II)

dimeric species upon reaction with triphenylphosphine. It was reported that the

carbonyl groups in species 68 were removed under vacuum before its reaction with

dioxygen. The phenol species 67，without coordinated carbonyl groups, reacted

analogously with dioxygen and gave products with similar spectroscopic properties.

Karlin and co-workers have modified the binucleating ligands 60-64 and

prepared the imsymmetrical ligand 71 (Scheme 16).

N C t C L b p + 0 ^ 广 3 ~~EtOAc ‘

H iH3

L _ 4 . ( X ^ X ^ N H 2 MeOH/AcO” QL ^ Et2〇 N f ^ ^ J

H3C /

o 71

(Scheme 16)

68

The binuclear copper(I) complex 72 was prepared by treating 71 with two

equivalents of the copper(I) precursor [Cu(CH3CN)4]+X- (X = PFe, CIO4) in

dichloromethane (Scheme 17). Complex 72 underwent hydroxylation reaction with

dioxygen in either DMF or acetonitrile to form the dioxygen-copper(II) intermediate

73，which has been characterized by X-ray crystallography.

py^ fPY 「 f \ 广

S g A hT 2 [Cu(CH3CN)4r (〒u' 广F Y H3 多 ( Y ^

71 72 」

PY = 2-Pyridyl O2, 0°C DMF or CH3CN

V V W Y S/ � L n _

74 73

O2, -78°C

CH2CI2

- ^ -|2+

OCX^CHs py-\~Cu；' /Ci/hhsicch3 V Y W

L 6H � 75

(Scheme 17)

69

The dicopper(I) complex 74 was prepared by reduction of dicopper(II) complex

73 with diphenylhydrazine. 74 has been characterized by two absorption bands in

the UV-Vis region at 312 nm and 366 nm. It reacted with dioxygen at -78 °C to give

(hydroperoxo)dicopper(II) complex 75, which has been characterized by a strong

absorption band at 390 nm (HOCT—Cii(II) LMCT transition), a shoulder at about

450 nm, and some weaker absorptions at about 630 nm and 1000 nm (d-d transition

for Cu(II)). Besides, complex 75 reacted with triphenylphosphine to yield

triphenylphosphine oxide (85%), a characteristic reaction for the hydroperoxo

complexes (Scheme 17).6a’ 6b

Karlin et al have reported a number of dinucleating ligands and the

corresponding dicopper-peroxo and -oxo complexes，； Some of them formed

(hydroperoxo)dicopper(II) complexes (76 and 77), converting triphenylphosphine to

triphenylphosphine oxide upon oxygenation，，6b’ 6d

- ^ 广「 ^ 2+

V V Vy� V 9 V L OH 」 L OH J

76 77

PY = 2-Pyridyl PY = 2-Pyridyl

70

Apart from dicopper complexes, dicopper-peroxo, -oxo and -hydroperoxo

derived from copper complexes containing mononucleating ligands could also be

prepared.

Suzuki and co-workers have reported a bis( i i -oxo)dicopper(III) complex 79

which was prepared by the reaction of the monomeric copper(I) complex 78 with

dioxygen in acetone/methanol (10:1) at -78 °C. 79 has been characterized by X-ray

crystallography, UV-Vis, and resonance Raman spectroscopy.^^ It is noteworthy that

a reversible conversion of 79 to 78 could be achieved by bubbling nitrogen gas into a

dichloromethane solution of 79 at -80�C (Scheme 18)/®

A fS f| CH2=2_8Q。C 0 M \ y O

u 》 ^ 办 78 79 (Scheme 18)

The bis( // -oxo)dicopper(III) complex 79 exhibited an isotope-sensitive band at

590 cm" with (564 cm' with in its resonance Raman spectrum measured

in acetone at -80 °C with a laser excitation at 488 nm. These characteristic bands

71

were similar to those observed for the bis(}i-oxo)dicopper(in) complexes."’ The

UV-Vis spectrum of 79 in dichloromethane at -80。C showed an intense absorption at

378 nm, a shoulder at about 490 nm, and two more bands at 258 nm and ca. 300 nm.

The solid state structure of 79 has been determined by X-ray crystallography, which

showed an average Cu-0 and Cu-Cu bond lengths of 1.803 A and 2.758 A,

respectively. Al l of the data were comparable to those of bis( // -oxo)dicopper(III)

complexes."’ ！之

Reaction of 79 with triphenylphosphine in acetone at -78。C under an argon

atmosphere gave dioxygen and the monomeric copper(I) complex 80 (Scheme 19).

\ \ / j f V ^ 形<!> ： 1 ^^^ 02 + 广

r f ^ N f cr \ acetone. -78。C ( T ^ h Y

0 力 79 80

(Scheme 19)

72

Tolman and co-workers have reported a series of bis( i i -oxo)dicopper

complexes derived from monomeric copper(I) complexes (81-83) with macrocyclic

ligands (Scheme

r f x ^ R 1

~ V ^ R [CU(CH3CN)4]X I ^ J ^ 一

V n ^ X=SbFe-orCI04- 乂

k [ ^

R = Me, iPr, CHsPh 81 R = Me

82 R = iPr

83 R = CH2Ph (Scheme 20)

Upon oxygenation of complex 82 at - 7 8 � C in dichloromethane,

peroxo)-dicopper(II) species 84 was obtained. This species could be converted to

bis(|i-oxo)-dicopper(II) species 85 in tetrahydrofliran (Scheme 21)." At -75 °C，the

UV-Vis spectrum of 84 exhibited two absorption bands at 366 nm and 510 nm whilst

85 showed two absorption maxima at 324 nm and 448 nm. The resonance Raman

spectra of these two species have been measured as frozen solutions at -196 °C, with

laser excitation at 514 nm. Species 84 showed a signal at 722 cm'' and the bis(|u-

oxo)-dicopper(II) species 85 gave a signal at 600 cm' in their resonance Raman

spec 仕 a. 14

73

r 乂 "T

2 j i d L V^Z、CCH3 r

似 O2, -78°C

\ T H F

一 - 2 + - ^ ^ 一 2 +

— _j ‘― — 84 85

(Scheme 21)

In this research work, by using the same ligands reported in Chapter 2, several

novel mono- and dimeric copper(I) complexes derived from HL^' ^ have been

prepared and characterized. Their reactivities toward dioxygen have also been

studied.

74


3-B. Preparation of Copper(I) Complexes with N^O Tetradentate Ligands

In recent years, Karlin et al，、^^ and Tolman et al.^^' ^^ have studied the

oxygenation reaction of a series of monomeric and dimeric copper(I) complexes,

derived from similar or the same macrocyclic ligands as those they used to prepare

model complexes for galactose oxidase.

Copper(I) salts, such as [Cu(CH3CN)4]PF6 '''' ^^ [Cu(CH3CN)4](C104) 6b’ 6〜

[C u (CH3CN)4] (S03CF3)15 were commonly used for the preparation of monomeric

and dimeric copper(I) complexes. These copper(I) salts contain weakly coordinating

anions so that coordination to the metal centers during oxygenation reactions may be

suppressed. Reduction of copper(II) complexes may also be an alternative route to

copper(I) complexes.

In this part of our studies, a series of copper(I) complexes have been prepared

using proligands 34-39. In our study, Cul, [Cu(CH3CN)4]PF6 and

[Cu(CH3CN)4](C104) have been used as starting materials for the preparation of the

corresponding complexes. The former one, with a strong coordinating anion, was

stable to air and thus easy to be handled. The latter two, with weakly coordinating

anions, resulted in an intactable oil or disproportionation.

75

Treatment of copper(I) iodide with compounds 34 or 35 and triethylamine in

tetrahydrofliran gave the bisO-I) dicopper(I) complexes 86 and 87，respectively

(Scheme 22). However, attempted synthesis of the corresponding dicopper(I)

compound derived from 36 was unsuccessful. Only a small amount of

uncharacterizable solid was obtained after the reaction. Both compounds 86 and 87

have been structurally characterized by X-ray crystallography.

(f^ A (T H O ^ ' 2. cu., THF

34 R = R- = t-Bu (HLI) 86 [Cu(HL^)(l)]2 (80%)

35 R = t-Bu, R' = H (Hl2) g? [Cu(HL2)(|)]2 (77%)

(Scheme 22)

It is noteworthy that attempted deprotonation of the phenol pendant using

triethylamine was unsuccessful. When stronger bases such as sodium hydroxide and

«-butyllithium were used, only a deep reddish brown intractable oil was obtained.

Attempted preparations of monomeric copper(I) complexes supported by 34-36，

starting from [Cu(CH3CN)4]PF6 and [Cu(CH3CN)4](C104) as the starting materials

were also unsuccessful.

76

Although the benzimidazole-containing proligands 37-39 are structurally similar

to the pyridine-based proligands 34-36, the structures of the copper(I) complexes

derived from these ligands are totally different. As shown in Scheme 23, compounds

37-39 reacted with copper(I) iodide to give the mononuclear three-coordinate

copper(I) complexes 88 and 89. Attempted preparation of copper complex derived

from 39 was unsuccessful.

H O ^ 2.CU,.THF HN 么广丨 R

3 7 R = R ' -Bu (Hl4)

38R = f-Bu, R' = H (Hl5) 88 Cu(HL^)l (61%)

39 R=H. R' = f-Bu (HL®) 89 Cu(HL5)| (22%)

(Scheme 23)

Being similar to 86 and 87, attempted deprotonation of the phenol pendant on

37 and 38 with triethylamine was unsuccessful.

Details of the preparation of compounds 86，87，88 and 89 are described in

Chapter 4 Experimental Section. These complexes have been characterized by NMR

77

spectroscopy, mass spectroscopy, in addition to X-ray crystallography. Their

reactivities toward dioxygen have also been investigated.

In our work, four copper(I) complexes (86，87，88 and 89) have been

successfully synthesized by using copper(I) iodide as the staring materials.

Conceivably, the iodide ion reduces the potential problem of disproportionation of

the copper(I) compounds.

7S

3-C. Characterization

3-C-L Structural Studies

The molecular structures of two bis(}a-iodo)dicopper(I) complexes [Cu(HL")0-

I)]2 (86，n= 1;87, « = 2) and the monocopper(I) complex [Cu(HL'^)I] (88), have been

determined by X-ray crystallographic analyses. Figures 32-34 show the molecular

structures of 86，87, and 88. Selected bond distances (A) and angles (。）for these

complexes are listed in Tables 11-13. Both the binuclear complexes 86 and 87

exhibit a tetrahedral N2I2 coordination geometry, whereas 88 exhibits a trigonal

planar N2I coordination geometry around the metal center. The Cu-Cu separations

fall in the range of 2.9-3.0 人.The Cu-I bond distances of 〜2.6-2.8 人 in the bisO-

iodo)-dicopper(I) complexes (86 and 87) are longer than that of 2.5136(8) A in the

monocopper(I) complex 88. Besides, the observed Cu-N bond lengths of 2.043(7)-

2.094(7) A in the dimeric copper(I) compounds 86-87 are also longer than that of

1.986(2) - 2.009(2) A in the monomeric copper(I) complex 88. The Cu(l)-I( l )

[2.5136(8)入]distance in 88 is similar to the observed Cu-I distance of 2.511(1)-

2.5335(9)人 in [(CuI)3L] (L = l,3,5-tris[bis(pyridin-2-ylmethyl)aminomethyl]-2,4,6-

triethylbenzene) reported by Kim et al.}^

79

A common structural feature observed among the three copper(I) complexes,

86，87 and 92 is that the tertiary amino groups of the ligand are not participating in

coordination to the copper center. It is generally believed that copper(I) prefers

tetrahedral coordination. Trigonal planar geometry has also been observed.

It is noteworthy that a mononuclear three-coordinate copper(I) complex (88)

was obtaining by employing the benzimidazole-containing ligand 37. This is in

contrast to the pyridine-based ligands 34 and 35，which gave rise to dicopper

complexes 86 and 87. Plausible reasons for the difference may be: (1) the

benzimidazole-containing ligand 37 is sterically more bulky than the pyridine-based

derivatives 34 and 35; (2) an interaction between adjacent molecules as observed in

the unit of cell of 88 (Figure 35).

80

^ \ V N ( 3 A ) ^ / C(7) h ec(17)

p - ^ N d A ) C(12)Q >C(9) C(24^C(25)

Figure 32. Molecular structure of [Cu(HL^)(|a-I)]2 (86) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 1 1 . Selected bond distances ( A ) and angles (。）for [Cu(HL^)(^-I)]2 (86).丰

Cul-CulA 2.9086(8) Cu l - I IA 2.6162(5)

Cul -N l 2.061(3) Cul-N2 2.063(3)

Cu l - I l 2.7817(5)

I l -Cu lA 2.6162(5) I l -Cu l -Cu lA 54.69(1)

Cu l - I l -Cu lA 65.12(1) N2-Cul-Nl 119.1(1)

N2-Cul-I1A 108.21(9) N l -Cu l - I IA 110.49(8)

N2-Cul- I l 97.43(9) N l -Cu l - I l 106.41(8)

I IA -Cu l - I l 114.87(1) N2-Cul-CulA 113.87(8)

N l -Cu l -Cu lA 125.81(7) I lA-Cu l -Cu lA 60.18(1)

* The numbers in parentheses are the estimated standard deviations in the last digit.

81

C(101

A

Figure 33. Molecular structure of [Cii(HL )(|i-I)]2 (87) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 12. Selected bond distances (A) and angles (。）for [Cu(HL^)(|a-I)]2 (87).*

Cul-CulA 3.029(2) Cul-N2 2.043(7)

Cu l - I l 2.625(1) Cu l - I IA 2.740(1)

Cul -N l 2.094(7)

I l -Cu lA 2.740(1) N2-Cul-Nl 118.9(3)

Cu l - I l -Cu lA 68.71(5) N l -Cu l - I l 106.5(2)

I l -Cul-N2 111.8(2) N l -Cu l - I IA 101.3(2)

I1A-Cul-N2 106.6(2) N2-Cul-CulA 125.5(2)

I l -Cu l - I IA 111.29(5) I l -Cu l -Cu lA 57.43(4)

N l -Cu l -Cu lA 115.0(2) I lA-Cu l -Cu lA 53.86(5)


82

C(5)

V

Figure 34. Molecular structure of [ C u ( H L 4 ) I ] (88) showing the atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 13. Selected bond distances (A) and angles (。）for [ C u ( H L 4 ) I ] (88).*

Cul- I l 2.5136(8) Cul-N3 1.986(2)

Cul-Nl 2.009(2)

Nl-Cul-N3 116.58(9) N3-Cul-I l 125.17(7)

N l -Cu l - I l 117.39(6)


83

禪 Figure 35. The interaction between two copper(I) complexes 88. Cu(lA)-N(2B): 3.468 A; I(1A)-N(2B): 3.575 A and Cu(lA)-N(2B)-I(lA): 66.8。.

84

3-C-II. Spectroscopic Studies

The copper(I) complexes 86, 87 and 88 have been flil ly characterized by

elemental analysis, mass spectrometry and NMR spectroscopy, in addition to single-

crystal X-ray crystallography. Complex 89 has been characterized by NMR

spectroscopy and LSI mass spectroscopy. However, correct elemental analysis of the

compound could not be obtained.

Both the mononuclear copper(I) compounds 88 and 89 have been characterized

by mass spectroscopy. The LSI spectrum of 88 showed the corresponding isotopic

ion distribution of the [M]+ species (Figure 36)，whilst that of 89 showed

fragmentation peaks due to the [M-I]+ species (Figure 37).

With a dio electronic configuration for copper(I), all of the copper(I) complexes

are not suitable for characterization with electron paramagnetic resonance (EPR).

The ^H and ^ C NMR spectra of the four copper(I) complexes (86，87, 88 and 89)

were obtained. Upon complexation, the two methylene protons located adjacent to

the pyridine or benzimidazole moiety of the ligands 34，35, 37 and 38 are chemically

and magnetically equivalent as they did not couple to each other and hence a singlet

was observed.

85

8 .Oe+06 -

6 . 0 e + 0 6 -

_� � I-O cr> cr> I—to CO o->

u-> 寸 ••O r-

•Kj- ».( }� 、0� -�.- JO 4 . 0e-»-06 •- fx? - c . •:、，

I.—.� ..“》 '.o '-O .o I ！

I i _ ：1� J�

2.0e+0;6 .. ；; ；1 ‘i� .�i�'1 ii ；丨 I. : I ；i I I

A h h ；; i\ V • .•..、•. , - .. , ••• -、.:.... . . ... 、 ... ，、. - ‘ ..... . • . .、 ’、 •‘...

O . O e + 0 0 _ 一 … … . . . • . I ： • • I , I • , ， I I -—-- . - r - - ,. -1 1 , 1

6 8 0 6 8 5 6 9 0 6 9 5 m / z

Figure 36. The LSI mass spectrum for [Cu(HL4)I] (88).

• • I • - - . . I... .-.i

2 Ce+08 ‘‘� 、.•••' •� f-••； VC3 ;• ‘ • r— r -

'.：_二 .：二 «•_； ‘--• 、-.• - - - •

Cli ':-••‘ •；�V.� cr-v T-�c、ro� -•J- • "-} •-t.t- TTf c--> ctj 、‘.•> r-'-. U-J iJ") U-)

- 、 S f ^ j 1 . 5 e + 0 8 —

l . O e + 0 8 - I

5 . 0 e + 0 7 I

i I i I I

_I. I I ； i I 1 :i LL_LJiLJJLi...L.丄“1..‘.....L...丄―丄.‘ —1 一..丄

U.Ce+OU 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 m / z

Figure 37. The LSI mass spectrum for [Cu(HL^)I] (89).

86

The NMR spectra of 88 and 89 showed THF signals that are consistent with

the presence of a lattice THF solvent molecule, as evidenced from the crystal

structure of 88. Figure 38 showed the NMR spectra of 89，in which the THF

signals were observed at 5 1.76 and 5 3.60.

E 2 Curr.ot Osta Parawters a • Nine eccO O

a f^ CD 卜卜 j ^ 、 r v r • • 卜卜〜 — 一一一一一

丨 ^ ^ ^ ^ 广厂二。 ‘ ’� I I 【『� n� I�1�a� I T f . F2 - Acquisition Parairoteps

Oate_ 20010319 riM 19.12 INSTflUM dtu300 PROBHO 5 m» Dual 13

t-BU PULPROG zg

M OS 0 n ^―-N \ SWH 8993.806 Hz

/ ^ FIOTES 0.274439 Hz . L ^ C U AO sec

H N ^ 恥进 niN J ow 55.600 usee

Oe 6.00 usee / )) TE 300.0 K (v J J 01 1.00000000 sec

.……••••• channel fl NUCl IH

‘ PI 4 . 5 0 u s e e PLl -2.00 06 SFOI 300.1312000 >*iz

F2 - Processing paraaeter， • SI 32768

SF 300.1300010 MHZ WOK EM ssa 0 LB 0.30 HZ C8 0 PC t.OO

to NMR pjot p»ra«ters I J CX 23.00 c«

. A l l 门P� 14.000 op»

L L__ J^ULm II___JUv Ts : .八 j\ 纖八八 A 二二二 c,

~� fy /oYm ml|oi| An /o\ HZCM 189.21239 Hz/cm

( T > 0 — C7101 (D (S o —� o j，” o� n�—. OT

I I I I I 11 r"r-i I ( I m r t i n j i~n~ri-n-r rrT i i i i i i > i | i i i i i i i i • -rn i n�ttvt•丁i�ti，i�i�i�i�i�i�i�i�titr�i�r pT n r • i ••••••• i • r'r r'T-|- ri i tti i r rTT.i丁ri,ri-’ r | n-rr-i • " i i • -i r' i't t i i i | r i i-i ppm 12 10 a 5 4 2 0

Figure 38. ^H NMR spectrum of[Cu(HL^)I] (89).

87

3-D. Reactivities of 86, 87 and 88 toward Dioxygen

The reactivities of copper(I) complexes toward dioxygen play an important role

in many biological processes」，、，Most of these processes involve dicopper systems.

In our studies, the reactivities of the binuclear copper(I) complex 86 toward dioxygen

have been studied. The oxygenation reaction was followed by an UV-Vis

spectrophotometer at -80 °C in order to identify the short-lived copper-dioxygen

intermediate. Figure 39 shows the changes of the UY-Vis spectra of an oxygenated

solution of 86 in dichloromethane from -80 °C to 10 °C. Absorption peaks at -320

nm, 420 nm and 600 nm were observed.

Upon oxygenation of 86 at -80 °C，a dark greenish brown solution was obtained,

which is believed to be due to a copper(II) species with absorption at 350 nm and

500 nm (Spectrum c, Figure 40). These absorptions are typical for copper(II) ion

with a d^ electronic configuration (Figure 40). Interestingly, this intermediate

species is stable at room temperature for about one day. Figure 40 summarizes the

spectra due to complex 86, an oxygenated intermediate, and the resultant reaction

product upon standing at room temperature for one day.

88

1.4『 8(fC

‘ ——-60'C 1.2 [ 50'C

丨一-40^C -——30'C

1 - - 2 0 ' C I 15'C [ -lO'C

n ；;c

I * ^ 。.4 Vm

jo 37。 . 0 . 0

wavelength (ran)

Figure 39. Changes of UV-Vis spectra of an oxygenated solution of 86 in dichloromethane from -80 to 10

89

- 1

1.75 A

i 1.25 戟 8 1 — \\ \ I 0.75 i \ V

- —"‘ I I - 一 - • 一 ^ , • — • • . - . - — •

〇一 • 、 ^ • • — • ^ 一广 • 一〜 — _ - — , , - , — —

1� “� I� ‘� ‘� ‘� ‘� I� ‘� “� ‘� ‘� I� ‘� “ I — I — I — I — — I — I — I — ] — 1 — I — I — 1 ~

^ 400 ^ 700 Wavelength (n

Figure 40. UV-Vis spectra of an oxygenated solution of 86 in dichloromethane. Spectrum a: -80。C; Spectrum b: 0 °C； Spectrum c: after standing at room temperature for 18 hours.

As shown in Figure 40，spectrum a represents the UV-Vis spectrum of the

reactive intermediate obtained upon oxygenation of 86 in dichloromethane at -80。C.

When the temperature of the solution was slowly raised, a red-shift of the absorption

spectrum was observed. Spectrum b shows the spectrum of the solution at 0 °C. The

absorption maxima at 330 nm and 350 nm on spectra a and b，respectively, were

assigned to the ligand-to-metal charge transfer (LMCT) bands. Presumably, the

absorptions at 410 nm and 600 nm might be due to a copper-hydroperoxo species. ' ^

90

u p o n standing at room temperature for 18 hours, both peaks at 410 nm and 600

nm disappeared (Spectrum c). A broad signal at 500 nm, however, was observed

which was assigned to be due to a copper(II) species.

Karlin and co-workers have reported that copper-hydroperoxo species could

oxidize triphenylphosphine to triphenylphosphine oxide. In order to prove the

possible formation of a hydroperoxo species upon oxygenation of 86，87 and 88，a

similar reaction has also been carried out.

Solutions of 86 and 87 in dichloromethane at -80 °C were bubbled with

dioxygen, followed by the addition of triphenylphosphine. After stirring 18 hours,

the resultant mixture was subjected to GC-MS analysis for triphenylphosphine oxide.

Interestingly, a quantitative conversion of triphenylphosphine to triphenylphosphine

oxide was observed. No oxo-transfer reaction was observed in control experiments,

in which no complex has been added. Complex 88，on the other hand, does not

facilitate the similar oxo-transfer reaction upon oxygenation with dioxygen. Results

of these experiments showed that a copper-hydroperoxo species may be the reactive

intermediate upon oxygenation of the binuclear complexes 86 and 87 at low

temperature.

Besides, the corresponding copper(II) species of both complexes in

dichloromethane after the reaction of 86 and 87 with triphenylphosphine were

91

characterized wi th UV-Vis spectroscopy at room temperature (Figure 41). Both

signals at 410 nm and 600 nm disappeared for both complexes. Only three

absorption bands were observed at 〜260 nm, 295 nm and 360 nm，which were

assigned to copper(n) species.

2 Cu(II species of 86

I 5 Cu仰 species of 87

I i | 、

0� ‘� I� ‘� ‘�

2： to 320 420 ^ 720

-0.5 -wavelengtti (nm)

Figure 41. UV-Vis spectra of oxygenated solutions of 86 and 87 in dichloromethane after reaction with triphenylphosphine.

92

3-E. Summary

In conclusion, two bis( {i -I) dicopper(I) complexes 86 and 87 were synthesized

successfully with the pyridine-based tripodal tetradentate ligands 34 and 35. X-Ray

crystallography revealed that both complexes 86 and 87 are binuclear with

tetrahedrally coordinated copper(I) centers. With benzimidazole-based ligands 37

and 38，two mononuclear copper(I) complexes 88 and 89 were successfully prepared.

X-Ray crystallography revealed a trigonal planar coordination geometry around the

copper center in 88.

Oxygenation reactions of the bis( i i -iodo) dicopper(I) compounds 86 and 87

have been monitored by UV-Vis spectroscopy at low temperatures. The

corresponding copper hydroperoxo species have been suggested as the reactive

intermediates in these reactions, as evidenced by the conversion of

triphenylphosphine to triphenylphosphine oxide.

On the other hand, no oxo-transfer to triphenylphosphine has been observed

upon the oxygenation of a dichloromethane solution of the three-coordinate copper(I)

complex 88 at low temperature.

93

3-F. References

1. Schindler, S. Eur. J. Inorg. Chem. 2000, 2311-2326.

2. Kopf，M. -A.; Karlin, K. D. In Biomimetic Oxidations Catalyzed by Transition

Metal Complexes; Meunier, B., Ed.; Imperial College Press: London, 2000;

Chapter 7，pp 309-362.

3. Karlin, K. D.; Zuberbuhler, A. D. In Bioinorganic Catalysis: Second Edition,

Revised and Expanded., Reedijk, J., Bouwman, E.，Eds.; Marcel Dekker: New

York, 1999; pp 469-534.

4. Sorrell, T. N.; Vankai, V. A. Inorg. Chem, 1990, 29, 1689-1692.

5. Murthy, N. N.; Mahroof-Tahir, M.; Karlin, K. D. Inorg. Chem. 2001，40, 628-635.

6. (a) Mahroof-Tahir, M.; Murthy, N. N.; Karlin, K. D.; Blackburn, N. J.; Shaikh, S.

N.; Zubieta, J. Inorg. Chem. 1992, 31, 3001-3003; (b) Karlin, K. D.; Ghosh, P.;

Cruse, R. W.; Farooq, A.; Gultneh, Y.; Jacobson, R. R.; Blackburn, N. J.; Strange,

R. W.; Zubieta, J. J. Am. Chem. Soc. 1988, 110, 6769-6780; (c) Zhang, C. X.;

Liang, H. C.; Kim, E. I.; Gan, Q. F.; Tyeklar, Z.; Lam, K. C.; Rheingold, A. L.;

Kaderli, S.; Zuberbuhler, A. D.; Karlin, K. D. Chem. Commun. 2001, 631-632; (d)

Karlin, K. D.; Cruse, R. W.; Gultneh, Y.; Farooq, A.; Hayes, J. C.; Zubieta, J. J ,

Am. Chem. Soc. 1987,109’ 2668-2679.

94

7. Paul, P. P.; Tyeklar, Z.; Jacobson, R. R.; Karlin, K. D. J. Am. Chem. Soc. 1991,

113, 5322-5332.

8. Liang, H. C.; Karlin, K. D.; Dyson, R.; Kaderli, S.; Jung, B.; Zuberbuhler, A. D.

Inorg. Chem. 2000，39, 5884-5894.

9. (a) Jacobson, R. R.; Tyeklar, Z.; Farooq, A.; Karlin, K. D.; Liu, S.; Zubieta, J. J .

r

Am. Chem. Soc. 1988, 110, 3690-3692; (b) Schatz, M.; Becker, M.; Thaler, F.;

Hampel. F.; Schindler, S.; Jacobson, R. R.; Tyeklar, Z.; Murthy, N. N.; Ghosh, P.;

Chen, Q.; Zubieta, J.; Karlin, K. D. Inorg. Chem. 2001, 40, 2312-2322.

10. Hayashi, H.; Fujinami, S.; Nagatomo, S.; Ogo, S.; Suzuki, M.; Uehara, A.;

Watanabe, Y.; Kitagawa, T. J. Am. Chem. Soc. 2000，122, 2124-2125.

11. Mahapatra, S.; Halfen, J. A•； Wilkinson, E. C.; Pan, G.; Wang, X.; Young, V. G.，

Jr.; Cramer, C. J.; Que, L.，Jr.; Tolman, W. B. J. Am. Chem. Soc. 1996，118,

11555-11574.

12. Mahadevan, V.; Hou, Z.; Cole, A. P.; Root, D. E.; Lai, T. K.; Solomon, E. I.;

Stack, T. D. P. J. Am. Chem. Soc. 1997,119, 11996-11997.

13. Lam, B. M. T.; Halfen, J. A.; Young, V. G.，Jr.; Hagadom, J. R.; Holland, P. L.;

Lledos, A.; Cucurull-Sanchez, L.; Novoa, J. J.; Alvarez, S.; Tolman, W. B. Inorg.

Chem. 2000, 39, 4059-4072.

95

14. Halfen, J. A.; Mahapatra, S.; Wilkinson, E. C.; Kaderli, S.; Young, V. G.，Jr.;

Que, L.，Jr.; Zuberbuhler, A. D.; Tolman, W. B. Science 1996，271, 1397-1400.

15. He, C.; DuBois, J. L.; Hedman, B.; Hodgson, K. O.; Lippard, S. J. Angew. Chem.

Int. Ed. 2001, 40, 1484-1487.

16. Walsdorff, C.; Park, S.; Kim, J.; Heo. J.; Park, K. -M.; Oh, J•； Kim, K. J. Chem.

Soc” Dalton Trans., 1999, 923-929.

17. Kitajima, N.; Moro-oka, Y. Chem. Rev. 1994，94, 737-757.

96

CHAPTER 4

Experimental Section

4-A. General Preparations and Physical Measurements

4-A-I. General Preparations

Al l reactions were carried under a purified nitrogen atmosphere using Schlenk-

line techniques. Solvents were distilled under nitrogen from sodium benzophenone

(tetrahydrofliran, toluene, diethyl ether) or calcium hydride (dichloromethane,

acetonitrile), and degassed twice by freeze-thaw cycles before use. Triethylamine

was distilled over sodium under a nitrogen atmosphere.

Al l reagents, unless otherwise indicated, were of analytical grade and were

used without further purification. iV,A^-Bis(2-pyridylmethyl)amine [BPMA]^ N,N-

bis(2-benzimidazolylmethyl)amine [BBA]^, and 3,5-di-^err-butyl-2-hydroxybenzyl

bromide〗 were prepared according to literature procedures.

97

4-A-IL Physical Measurements

1h NMR (300 MHz) and ^ C NMR (75.4 MHz) spectra were obtained on a

Bruker DPX 300 spectrometer. LSI mass spectra were obtained on a Bruker APEX

47e Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. EI mass

spectra were measured by a Hewlett-Packard 5989B Mass Engine spectrometer.

Elemental analyses were performed by MED AC Ltd., Brunei University, U. K.

Melting point was measured by Electrothermal 9100 digital melting point apparatus.

EPR analyses were performed by Bruker EMX-EPR spectrometer equipped with a

helium-flow cryostat (Oxford Instrument). UV-Vis spectra were obtained on a Gary

5E UV-Vis-NIR spectrophotometer or a Beckman DU-7500 photo-diode array

spectrophotometer. Low-temperature UV-Vis spectra were obtained on a Hewlett-

Packard 8453 UY-Vis spectrophotometer. GC-MS spectra were obtained by a

Hewlett-Packard 6890 GC - 5973 MSD system.

98

4-B. Compounds Described in Chapter 2

Preparation of Di-Substituted Amines

iV,iV-Bis(2-pyridylmethyl)amine [BPMA] (49). To a solution of 2-

pyridinecarboxaldehyde (0.11 g, 1.0 mmol) in methanol was added a solution of 2-

aminomethylpyridine (0.11 g, 1.0 mmol) in methanol. A dark brown mixture was

obtained immediately. After stirring overnight, sodium borohydride (0.076 g, 2.0

mmol) was added slowly to yield a pale yellow solution. Stirring was continued for

another 2 hours. Al l the volatiles were removed under reduced pressure and water

was added. The mixture was neutralized with concentrated hydrochloric acid

followed by extraction with dichloromethane. The combined extracts was dried over

anhydrous magnesium sulphate and rotary evaporated to give a yellow oily liquid.

Yield: 0.18 g (90 %). tf NMR (CDCI3): 5 8.50 (d，J= 4.8 Hz, 2 H, pyridyl), 7.58 (t,

J = 7.7 Hz, 2 H，pyridyl), 7.30 (d, •/= 7.5 Hz, 2 H, pyridyl), 7.10 (t, J = 7.7 Hz, 2 H，

pyridyl), 3.93 (s, 4 H, CH2), 3.21 (br, 1 H，NH).

7V,A^-Bis(2-benzimi(lazolylmethyl)amine [BBA] (50). A mixture of iminodiacetic

acid (6.66 g, 50 mmol) and o-phenylenediamine (10.8 g，100 mmol) was heated at

200。C in a capped round-bottom flask to give a dark purple solid. It was grounded

with a mortar and then extracted in refluxing methanol for about 18 hours. The

99

solution was filtered and the purple-red filtrate was concentrated. Recrystallization

of the crude product from diethyl ether gave 50 as a white solid. Yield: 7.0 g (50 %).

Hi NMR (CD3OD): 5 7.53 (m, 4 H, Ar), 7.22 (m, 4 H, Ar), 4.11 (s, 4 H, CH2).

Preparation of Substituted Benzaldehydes

3，5-Di-,忍"-butyI-2-hydroxybenzaldehyde (40). To a solution of 1>,5-6i-tert-

butylphenol (2.10 g, 10.0 mmol) and tributylamine (0.95 ml, 4.0 mmol) in toluene

was added SnCU (0.12 ml, 1.0 mmol) dropwise under nitrogen. A white fiime

appeared immediately during the addition and stirring was continued for 15 minutes

at room temperature. Paraformaldehyde (0.66 g, 22.2 mmol) was then added in a

single portion and the mixture was refluxed overnight. Water was added and the

residue was extracted with diethyl ether. The combined extracts were evaporated to

dryness. After purification by column chromatography, a pale yellow solid was

obtained. Yield: 1.90 g (80 %). ^H NMR (CDCI3): 6 9.87 (s, 1 H, CHO), 7.60 (d, J

=2 .4 Hz, 1 H, Ar), 7.35 (d, J = 2.4 Hz, 1 H, Ar), 1.43 (s, 9 H，/-Bu), 1.33 (s，9 H, t-

Bu).

3-r^i^-Butyl-2-hydroxybenzaldehyde (41). This was prepared analogously as for

compound 40, starting with using 3-^er^-butylphenol (1.50 g, 10.0 mmol). Yield:

100

1.30 g (72 %). ^H NMR (CDCI3): 5 9.87 (s, 1 H, CHO), 7.53 (dd，《/= 1.7, 7.7 Hz, 1

H, Ar), 7.39 (dd, J=L7, 7.7 Hz, 1 H, Ar), 6.94 (t, 7.7 Hz, 1 H, ArH), 1.42 (s, 9 H,

Bu).

5-^^#t-Butyl-2-hydroxybenzaldehyde (42). This was prepared analogously as for

compound 40，starting with 5-/err-butylphenol (1.50 g, 10.0 mmol). Yield: 1.24 g

(70 %). ^H NMR (CDCI3): 5 9.89 (s, 1 H，CHO), 7.59 (dd, J = 2.4，8.7 Hz, 1 H, Ar),

7.52 (d，J= 2.4 Hz, 1 H, Ar), 6.94 (d, J= 8.7 Hz, 1 H，^Bu), 1.33 (s, 9 H, /-Bu).

Preparation of Substituted Benzyl Alcohols

3,5-Di-r忍"-butyl-2-hydroxybenzyl alcohol (43). To a solution of compound 40

(0.23 g, 1.0 mmol) in methanol was slowly added sodium borohydride (0.08 g, 2.0

mmol). The pale yellow solution was stirred overnight and then evaporated to

dryness. Water was added to dissolve the residue. The mixture was neutralized with

hydrochloric acid and then extracted with dichloromethane. The combined extracts

was pumped to dryness to give a yellow oil which was used directly without further

purification. Yield: 0.23 g (95 %).

101

3-^^/t-Butyl-2-hydroxybenzyl alcohol (44). This was prepared analogously as for

compound 43，starting with compound 41 (0.18 g，1.0 mmol). Yield: 0.17 g (93 %).

5-^^r^-Butyl-2-hydroxybenzyl alcohol (45). This was prepared analogously as for

compound 43，starting with compound 42 (0.18 g, 1.0 mmol). Yield: 0.17 g (96 %).

Preparation of Benzyl Bromides

3，5-Di-,衫"-butyl-2-hydroxybenzyl bromide (46)。To a solution of compound 43

(0.24 g，1.0 mmol) in chloroform was added phosphorus tribromide (0.10 ml, 1.0

mmol). A white fume appeared during the addition and stirring was continued for an

hour. The resultant solution was quenched with cold water. The aqueous layer was

extracted with chloroform. The combined extracts was evaporated to dryness to give

a pale yellow oily liquid which was used directly without further purification. Yield:

0.29 g (95 %).

3-^^/t-Butyl-2-hydroxybenzyl bromide (47). This was prepared analogously as for

compound 46, starting with compound 44 (0.18 g, 1.0 mmol). Yield: 0.23 g (96 %).

102

5-,忍"-Butyl-2-hydroxybenzyl bromide (48). This was prepared analogously as for

compound 46’ starting with compound 45 (0.18 g，1.0 mmol). Yield: 0.23 g (96 %).

Preparation of Tetradentate Ligands

[A^-(3,5-Di-^^rr-butyl-2-hydroxybenzyl)-AyV-di-(2-pyridylmethyl)]ainine [HL^]

(34). A solution of 3,5-di-^er^-buty 1-2-hydroxylbenzy 1 bromide 46 (0.30 g, 1.0

mmol) in THF was added dropwise to a solution of BPMA 49 (0.20 g, 1.0 mmol) in

THF under nitrogen. After stirring for 5 min., triethylamine (0.15 mL，1.1 mmol)

was added. The mixture was refluxed overnight. After cooling down to room

temperature, the resulting yellow suspension was filtered. The filtrate was

concentrated under reduced pressure and purified by column chromatography using

ethyl acetate as eluent. The third band was collected. Al l the volatiles were removed

under reduced pressure to give a yellow solid. Yield: 0.35 g (84 %). M.p.: 81-82 °C.

1h N M R (CDCI3): (5 = 8.55 (d，J= 7.8 Hz, 2 H, pyridyl)，7.61 (dt, J= 1.8, 7.8 Hz, 2

H, pyridyl), 7.37 (d, J = 7.8 Hz, 2 H, pyridyl), 7.22 (d, J= 2.4 Hz, 1 H, Ar), 7.11-

7.15 (m，2 H，pyridyl), 6.89 (d, J= 2A Hz, 1 H, Ar), 3.88 (s, 4 H, CH2), 3.81 (s, 2 H,

CH2), 1.47 (s, 9 H，^Bu), 1.27 (s, 9 H, t-Bu). NMR (CDCI3): 5 = 158.0，

153.7, 148.9, 140.2，136.5，135.4，124.4, 123.5, 123.0, 122.1, 121.6, 59.4，58.1，34.9,

34.0, 31.6，29.5. HRMS (LSI): m/z 418.2847 (calcd. for C27H35N3O [MH]+

103

418.2853).

[^-(3-^^ft-Butyl-2-hydroxybenzyl)-AVV-di-(2-pyridylmethyl)] amine [HL^] (35).

This was prepared analogously as for 34，starting with 3 -^er/-butyl-2-hydroxylbenzyl

bromide 47 (0.24 g, 1.0 mmol). Yield: 0.29 g (80 %). M.p.: 75-76 °C. ^H NMR

(CDCI3): 5 = 8.56 (d,J= 6.6 Hz, 2 H，pyridyl), 7.63 (dt, J = 1.2，7.7 Hz, 2 H,

pyridyl)，7.36 (d，J= 7.4 Hz, 2 H, pyridyl), 7.14-7.21 (m，3 H, pyridyl and Ar), 6.92

(dd，J= 0.7，7.3 Hz, 1 H, Ar), 6.71 (t ,y=7.5 Hz, 1 H, pyridyl), 3.87 (s，4 H, CH2),

3.82 (s，2 H, CH2), 1.46 (s, 9H，/-Bu). NMR (CDCI3): (5 = 157.9，156.4,

148.8, 136.7, 128.0，126.2，123.5，122.6，122.2，118.2, 59.2，57.7, 34.7，29.5. HRMS

(LSI): m/z 362.2221 (calcd. for C23H28N3O [MH]+ 362.2227).

[A^-(5-r^rr-Butyl-2-hy(lroxylbenzyl)-iV^-di-(2-pyridylmethyl)] amine [HL^] (36).

This was prepared analogously as for 34，starting with 5-rer^butyl-2-hydroxylbenzyl

bromide 48 (0.24 g, 1.0 mmol). Yield: 0.28 g (78 %). M.p.: 76-78。C. ^H NMR

(CDCI3): 5 = 8.57 (d，J = 7.5 Hz, 2 H, pyridyl), 7.63 (dt, J= 1.8, 7.7 Hz, 2 H,

pyridyl), 7.37 (d，J= 7.8 Hz, 2 H，pyridyl), 7.14-7.21 (m, 3 H, pyridyl and Ar), 7.04

(d，J= 2.4 Hz, 1 H, At), 6.84 (1,7= 8.4 Hz, 1 H, pyridyl), 3.90 (s, 4 H, CH2), 3.79 (s，

2 H，CH2), 1.27 (s，9 H, t-Bu). NMR (CDCI3): 5 = 158.2, 155.0, 148.8，

141.1，136.8, 126.9，125.7, 123.2，122.2, 121.8，115.8, 59.1, 57.4，33.8, 31.5. HRMS

104

(LSI): m/z 362.2244 (calcd. for C23H28N3O [MH]+ 362.2227).

[AyV-Di-(2-benzimidazolylmethyl)-iV"(3，5-di-/忍"-butyl-2-hydroxylbenzyl)]amine

[HL4] (37). A solution of 3,5-di-^er^butyl-2-hydroxybenzyl bromide 46 (0.30 g, 1.0

mmol) in THF was added dropwise to a solution of BBA (50) (0.28 g, 1.0 mmol) in

THF under nitrogen. After stirring for 5 min.，triethylamine (0.15 mL, 1.1 mmol)

was added. The mixture was refluxed overnight. The resulting reddish brown

suspension was cooled down and then filtered. The filtrate was concentrated under

reduced pressure and purified by column chromatography using ethyl acetate as

eluent. The third band was collected and evaporated to give 37 as a pink solid.

Yield: 0.25 g (50 %). ^H NMR (DMSO-de): (5 = 12.41 (s，2 H，NH)，10.73 (s，1 H，

OH), 7.61 (m，4H, Ar), 7.18 (m, 4 H，Ar), 7.10 (s，1 H, Ar) , 6.04 (s, 1 H, Ar) , 4.11 (s,

4H, CH2), 3.92 (s, 2 H, CH2), 1.40 (s，9 H, /-Bu), 1.21 (s, 9 H, t-Bu). NMR

(DMSO-de): 5 = 153.6, 151.6, 142.8，139.6，134.9，134.0，125.4，122.5, 122.2，

122.0，121.4，118.4, 111.4, 55.6，50.2, 34.7, 33.8, 31.5, 29.7. HRMS (LSI): m/z

496.3210 (calcd. for C31H37N5O [MH]+ 496.3595). Anal. Calcd. for

C31H37N5O • CH3COOCH2CH3： C, 72.00; H, 7.77; N, 12.00 %. Found: C, 72.62; H，

7.74; N, 12.630/0.

105

[iV^-Di-(2-benzimidazolylmethyl)-A^-(3-/^/t-butyl-2-hydroxylbenzyl)]amine

HL^] (38). This was prepared analogously to HL* 37, starting with 3-/er^butyl-2-

hydroxybenzyl bromide 47 (0.24 g, 1.0 mmol). Yield: 0.18 g (40 %). ^H NMR

(CD3OD): (5 = 7.54 (m, 4 H, Ar), 7.22 (m, 4 H, Ar), 7.05 (dd，J= 1.5, 7.8 Hz, 1 H，

Ar), 6.90 (dd ,y= 1.5, 7.4 Hz, 1 H，Ar), 6.64 (t, 7.8 Hz, 1 H，Ar), 4.04 (s, 4 H,

CH2), 3.83 (s, 2 H, CH2), 1.33 (s，9 H，f-Bu). NMR (CD3OD): 5 = 156.9,

152.4, 139.4, 137.8，129.2，127.4，123.7, 123.3, 120.0，115.8，58.8，52.8, 35.5，30.1.

HRMS (LSI): m/z 440.2454 (calcd. for C27H29N5O [MH]+ 440.5615). Anal. Calcd..

for C27H29N5O: C, 73.78; H，6.65; N, 15.93 %. Found: C, 73.36; H, 6.71; N, 15.44

%.

[AyV-Di-(2-benzimidazolylmethyl)-7V-(5-/^i^-butyl-2-hydroxylbenzyl)]amine

[ h i / ] (39). This was prepared analogously to H i / 37, starting with S-tert-hutyX-l-

hydroxybenzyl bromide 48 (0.24 g, 1.0 mmol). Yield: 0.16 g (36 %). ^H NMR

(CD3OD): 6 = 7.54 (m, 4 H, Ar), 7.23 (m, 4 H, Ar), 7.15 ( d , / = 2.4 Hz, 1 H, Ar),

7.09 (dd,y= 2.4，8.4 Hz, 1 H, Ar), 6.72 (d, •/= 8.4 Hz, 1 H, Ar), 4.04 (s, 4 H, CH2),

3.83 (s, 2 H，CH2), 1.21 (s, 9 H，/-Bu). NMR (CD3OD): (5 = 155.0，153.7,

143.3, 139.3，129.1, 126.9’ 123.5, 123.1，116.5，115.7，56.4，53.1, 34.7’ 31.9. HRMS

(LSI): m/z 440.2409 (calcd. for C27H29N5O [MH]+ 440.5615). Anal. Calcd. for

C27H29N5O • CH3COOCH2CH3： C, 70.56; H, 7.07; N，13.27 %. Found: C, 70.33; H,

106

6.90; N , 1 3 . 6 5 % .

Preparation of Copper(II) Complexes

[Cu(HL^)Cl]Cl (51). A solution of CuCl] (0.13 g, 1.0 mmol) in methanol was added

to HL^ (34) (0.42 g, 1.0 mmol) in the same solvent to afford a deep blue solution.

Triethylamine (0.14 mL, 1.0 mmol) was then added dropwise with stirring to give a

deep purple solution. The solution was refluxed for 2 hours and the resulting

suspension was cooled down and then filtered. Al l the volatiles were removed under

reduced pressure to give a deep purple solid. Recrystallization from

dichloromethane afforded blue crystals suitable for X-ray structural analysis. Yield:

0.44 g (80 %). M.P.: 213-214。C (dec.). HRMS (LSI): m/z 517.1734 (calcd. for

C27H36CIC11N3O [M-C1]+ 517.3528). Anal. Calcd. for C27H35CI2CUN3O • H2O: C，

56.88; H, 6.54; N, 7.37 %. Found: C, 56.24; H，6.60; N，7.17 %.

[CU(HL^)(CH3COO)1(CH3COO) (52) . Triethylamine (0.14 mL, 1.0 mmol) was

added dropwise to a solution of HL^ (34) (0.42 g，1.0 mmol) in methanol, followed

by a solution of Cu(CH3COO)2 • H2O (0.20 g, 1.0 mmol) in methanol. The resulting

deep purple solution was stirred overnight and then filtered. The filtrate was

evaporated under reduced pressure. Recrystallization from ethyl acetate afforded

107

blue needle-shaped crystals suitable for X-ray structural analysis. Yield: 0.30 g (50

%). M.p.: 96-97 °C (dec.). Anal. Calcd. for C31H41CUN3O5 • CH3COOCH2CH3： C,

61.14; H, 7.19; N，6.12 %. Found: C, 60.31; H, 6.87; N, 6.27 %.

Cu(L^)Cl (53). 1 M NaOH (1.0 mL, 1.0 mmol) in water was added to a solution of

HL^ ( 3 4 ) (0.420 g，1.0 mmol) in methanol to afford a yellow solution. A solution of

C11CI2 (0.14 g, 1.0 mmol) in methanol was then added drop wise. The solution was

stirred overnight and the resulting suspension was filtered. The filtrate was

evaporated under reduced pressure to give a purple solid. Yield: 0.38 g (73 %).

M.P.: 191-192 °C (dec.). HRMS (LSI): m/z 515.1759 (calcd. for C27H34N3OCUCI

[M]+ 515.2681). Anal. Calcd. for C27H34CIC11N3O • O.5H2O: C, 61.82; H, 6.73; N，

8.01 %. Found: C，61.84; H, 6.68; N, 7.94 %.

CU(L^)(CH3COO) (54). This was prepared analogously as for Cu(L^)Cl 53，starting

with Cu(CH3COO)2 • H2O (0.20 g，1.0 mmol). Recrystallization from acetone

afforded deep red block-shaped crystals suitable for X-ray structural analysis. Yield:

0.43 g (80 %). M.P.: 177-178 °C. Anal. Calcd. for C29H37CUN3O • H2O: C, 62.51;

H, 7.06; N，7.54 %. Found: C, 62.74; H，7.29; N, 7.54 %.

108

Preparation of Zinc(II) Complexes

Zn(L^)Cl (55) . 1 M NaOH (1.0 mL, 1.0 mmol) in water was added to a solution of

HLI (34) (0.42 g，1.0 mmol) in methanol to afford a yellow solution. A solution of

ZnCl2 (0.141 g，1.0 mmol) in methanol was then added dropwise. The solution was

stirred overnight and the resulting suspension was filtered. The filtrate was

evaporated under reduced pressure to give a yellow solid. Recrystallization from

acetonitrile afforded colorless block-shaped crystals suitable for X-ray structural

analysis. Yield: 0.37 g (71 %). M.p.: 199-200 °C (dec.). ^H NMR (CD3OD): d =

9.16 (d ,y= 4.8 Hz, 2 H, pyridyl), 7.98 (dt，《/= 1.8，7.6 Hz, 2 H, pyridyl), 7.54 (t, J =

6.9 Hz, 2 H, pyridyl), 7.46 (d，/= 7.8 Hz, 2 H, pyridyl), 7.07 (d, J= 2.7 Hz, 1 H, Ar),

6.92 (d, J= 2.7 Hz, 1 H, Ar), 4.14 (d, J= 16.5 Hz, 2 H, CH2), 4.06 (d, J= 16.5 Hz, 2

H, CH2), 3.76 (s, 2 H，CH2), 1.36 (s, 9 H, /-Bu), 1.21 (s，9 H, /-Bu). ^ C NMR

(CD3OD): (5 = 163.0，157.3，150.5, 141.7，140.3’ 138.1，126.9, 125.1，124.9，124.8，

60.3, 58.8, 36.0, 34.7, 32.2, 30.7. HRMS (LSI): m/z 518.1694 (calcd. for

C27H34ClN30Zn [MH]+ 518.1627). Anal. Calcd. for C27H34ClN30Zn: C, 62.68; H,

6.62; N, 8.12 %. Found: C, 62.54; H, 6.68; N，8.01 %.

Zn(L2)Cl (56) . This was prepared analogously to Zn(L^)Cl (55), starting with HL^

(35) (0.36 g, 1.0 mmol). Recrystallization from acetone afforded colorless needle-

109

shaped crystals suitable for X-ray structural analysis. Yield: 0.29 g (56 %). M.p.:

205-206 °C (dec.). ^H NMR (CDCI3): (5 =6.41 (d, J= 4.8 Hz, 2 H，pyridyl), 7.82 (t,

J= 7.6 Hz, 2 H, pyridyl), 7.41 ( t ， 6 . 4 Hz, 2 H，pyridyl), 7.27 (d, J= 7.7 Hz, 2 H,

pyridyl), 7.11 (d，《/=7.6 Hz, 1 H, Ar), 6.84 ( d d , / = 1.3,7.2 Hz, 1 H, Ar), 6.38 (t，《/ =

7.4 Hz, 1 H, At), 4.09 (d, J= 15.0 Hz, 2 H，CH2)，3.86 (d，J= 15.0 Hz, 2 H, CH2),

3.78 (s, 2 H, CH2), 1.42 (s, 9 H，fBu). ^ C NMR (CDCI3): (5 = 155.0, 150.5，140.5,

139.9，129.1，126.8, 124.2, 123.2, 122.7，112.8, 59.3, 57.7, 34.9，29.6. Anal. Calcd.

for C23H26ClN30Zn: C, 59.88; H, 5.68; N，9.10 %. Found: C，59.70; H，5.87; N，

8.80 % .

Zn(L^)Cl (57) . This was prepared analogously to Zn(L^)Cl (55)，starting with HL^

(36) (0.36 g, 1.0 mmol). Recrystallization from dichloromethane afforded colorless

needle-shaped crystals suitable for X-ray structural analysis. Yield: 0.26 g (51 %).

M.P.: 203-205 °C (dec.). ^H NMR (CD3OD): (5 = 8.82 (s, 2 H, pyridyl), 7.99 (dt, J=

1.8，7.8 Hz, 2 H, pyridyl), 7.49 (t, 7.8 Hz, 4 H, pyridyl), 7.08 (s, 1 H, Ar), 6.98

(dd, J= in, 8.7 Hz, 1 H，Ar), 6.57 (d, J= 8.4 Hz, 1 H，Ar), 4.23 (d, J= 16.2 Hz, 2 H,

CH2), 4.15 (d, J = 16.2 Hz, 2 H, CH2)，1.23 (s, 9 H, t-Bu). ^ C NMR (CD3OD): 5 =

157.1，149.9’ 141.9，140.1, 129.3，127.9，125.5, 125.3, 123.1, 120.4，60.2’ 59.1，34.5，

32.1. Anal. Calcd. for CzsHzeClNsOZn: C, 59.75; H, 5.89; N，9.08 %. Found: C，

110

59.46; H, 5.66; N, 8.95 %.

Zn(L^)(CH3COO) (58). 1 M NaOH (1.00 mL, 1.0 mmol) in water was added to a

solution of HL^ (34) (0.420 g, 1.0 mmol) in methanol to afford a yellow solution. A

solution of Zn(CH3COO)2 • 2H2O (0.22 g，1.0 mmol) in methanol was then added

dropwise. The solution was stirred overnight and the resulting suspension was

filtered. The filtrate was evaporated under reduced pressure to give a yellow solid.

Recrystallization from acetone afforded colorless block-shaped crystals suitable for

X-ray structural analysis. Yield: 0.42 g (77 %). M.p.: 216-217 °C (dec.). ^H NMR

(CD3OD): (5 = 8.66 (d, 5.1 Hz, 2 H, pyridyl), 7.92 (dt, J = 1.8, 7.6 Hz, 2 H，

pyridyl), 7.46 ( t ， 6 . 6 Hz, 2 H, pyridyl), 7.38 (d, 7.8 Hz, 2 H，pyridyl), 6.97 (d,

J = 2.4 Hz, 1 H, Ar), 6.89 (d, J = 2.4 Hz, 1 H, Ar), 4.26 (d，•/= 16.5 Hz, 2 H，CH2)’

4.19 (d ,y= 16.5 Hz, 2 H, CH2), 3.73 (s，2 H, CH2)，2.08 (s, 3 H，CH3)’ 1.34 (s, 9 H,

/-Bu), 1.18 (s，9 H, ^Bu). 13c NMR (CD3OD): 5 = 180.6，163.3, 157.1，149.5，

1 4 1 . 3 ’ 139.4，138.0’ 127.0，125.1’ 1 2 4 . 9 , 124.7，124.3，61.1，60.1，36.0, 34.6，32.2,

30.6. Anal. Calcd. for CsgHsvNsOZn • H2O : C, 62.31; H, 7.03; N, 7.51 %. Found:

C，63.14; H，6.86; N, 7.58 %.

I l l

Zn(L^)(CH3COO) (59). This was prepared analogously to Zn(L^)(CH3C00) (58)，

starting with HL^ (35) (0.36 g, 1.0 mmol). Recrystallization from a mixed solvent of

chloroform and ethyl acetate (3:1) afforded colorless block-shaped crystals suitable

for X-ray structural analysis. Yield: 0.27 g (55 %). M.p.: 202-203 °C (dec.). ^H

NMR (CD3OD): 5 = 8.69 (d, J = 5.4 Hz, 2 H, pyridyl), 7.93 (dt, J = 1.8, 7.7 Hz, 2

H, pyridyl), 7.48 (t，J二 6.6 Hz, 2 H, pyridyl), 7.40 (d，J= 7.8 Hz, 2 H, pyridyl), 6.93

(dd, J= 1.8, 7.7 Hz, 1 H, Ar), 6.87 (dd, / = 1.8，7.5 Hz, 1 H，Ar), 6.32 (t, J = 7.5 Hz,

1 H, Ar), 4.26 (d, J = 16.5 Hz, 2 H，CH2), 4.19 (d, 16.5 Hz, 2 H, CH2)，3.73 (s, 2

H，CH2), 2.10 (s, 3 H，CH3), 1.34 (s, 9 H, ^ C NMR (CD3OD): 5 = 180.6，

166.1, 157.1，149.5, 141.4，140.6，130.5, 128.0, 125.6, 125.1，124.4, 115.8, 60.6,

59.9，35.7，30.5，23.7. Anal. Calcd. for C25H29N30Zn • 2CH3OH : C, 59.02; H, 6.74;

N, 7.65 %. Found: C，58.51; H，6.12; N, 8.18 %.

112

4-C. Compounds Described in Chapter 3

Preparation of Dimeric Copper(I) Complexes

[Cu(Hl/)(//-!)】2 (86). Triethylamine (0.14 mL, 1.0 mmol) was added dropwise to

a solution of HL! (34) (0.42 g, 1.0 mmol) in dry THF at 0。C under nitrogen. The

resulting yellow solution was stirred for 15 min. and then added dropwise to a slurry

of Cul (0.191 g, 1.0 mmol) in dry THF at 0 °C to give a bright yellow mixture. The

mixture was stirred overnight and then filtered. The yellow filtrate was evaporated

in vacuo to give compound 86 as a yellow solid. Recrystallization of the crude

product from dry dichloromethane afforded colorless block-shaped crystals suitable

for X-ray structural analysis. Yield: 0.48 g (80 %). M.p.: 162-163 °C. ^H NMR

(C6D6): 5 = 10.46 (s，2 H, OH), 9.35 ( d , y = 3.0 Hz, 4 H, pyridyl), 7.54 (dt，J= 3.0

Hz, 2 H, Ar), 6.94 ( d t， 2 . 0 ’ 7.5 Hz, 4 H，pyridyl), 6.79 (m, 6 H, Ar and pyridyl),

6.59 ( t , y = 6.0 Hz, 4 H，pyridyl), 3.87 (s，8 H，CH2), 3.45 (s，4 H, CH2)，1.75 (s, 18

H, /-Bu), 1.33 (s，18 H, t-Bu). '^C N M R (CeDg): (5 = 156.2, 154.8，151.9, 141.2,

137.0’ 136.3，125.9, 124.8，123.6, 123.1, 121.7，58.7，56.1，35.4，34.4, 32.0, 30.1.

Anal. Calcd. for C54H70I2N6O2CU2 • 2CH3OH: C, 52.54; H, 6.14; N，6.56 %. Found:

C, 52.42; H, 6.28;N, 6.17%.

113

[Cu(HL^)( n -I)]2 (87). This was prepared analogously to [Cu(HL^)(/z-I)]2 (86),

starting with HL 35 (0.36 g, 1.0 mmol). Recrystallization from dry dichloromethane

afforded colorless block-shaped crystals suitable for X-ray structural analysis. Yield:

0.85 g (77 %). M.P.: 167-169�C. ^H NMR (CsDe): d = 10.56 (s’ 2 H, OH), 9.29 (d,

J = 6.0 Hz, 4 H, pyridyl), 7.33 (dd，J= 1.5, 9.0 Hz, 2 H, Ar), 6.90 (dt，J二 1.5, 7.5

Hz, 4 H, pyridyl), 6.79 (d，•/= 7.5 Hz, 2 H, Ar), 6.74 ( d , J = 7.8 Hz, 4 H，pyridyl),

6.61 (dd, J 二 1.2，7.5 Hz, 2 H, Ar), 6.56 (t, 6.6 Hz, 4 H, pyridyl), 3.75 (s，8 H,

CH2), 3.36 (s，4 H, CH2)，1.68 (s，18 H，PBu). ^ C NMR (CeDe): S = 157.5，156.4，

152.1, 137.5，137.3, 127.3，126.0, 123.4，122.6, 119.5, 58.4，56.4，35.4, 30.3. Anal.

Calcd. for C46H54I2N6O2CU2： C，50.05; H, 4.93; N，7.61 %. Found: C，49.61; H,

5.07; N, 6.99 %.

114

Preparation of Monomeric Copper(I) Complexes

Cu(HL4)I (88). Triethylamine (0.14 mL, 1.0 mmol) was added dropwise to a

solution of HL4 (37) (0.50 g, 1.0 mmol) in dry THF at 0 °C under nitrogen. The

resulting yellow solution was stirred overnight and then added dropwise to a slurry of

Cul (0.19 g, 1.0 mmol) suspended in dry THF at 0 °C to give an orange solution. The

mixture was stirred overnight and then filtered. The orange filtrate was concentrated

in vacuo to afford 88 as colorless crystals suitable for X-ray structural analysis.

Yield: 0.42 g, 61 %. M.p.: 230-232。C. ^H NMR (DMSO-de): 6 = 13.10 (s, 2 H,

NH), 9.26 (s，1 H, OH), 8.43 (s, 2 H, Ar), 7.60 (m, 2 H, Ar), 7.32 (m，4 H, Ar), 7.18

(d, J = 3.0 Hz, 1 H, Ar) , 7.01 { d , J = 3.0 Hz, 1 H，Ar), 4.04 (s, 4 H, CH2), 3.90 (s，2

H, CH2), 1.41 (s, 9 H, t-Bu). 13c NMR (DMSO-de): 5 = 153.4，150.1，141.6，140.6，

135.3, 133.2, 124.6，123.5，122.8, 122.3, 121.2，119.3, 112.0，67.0, 57.6，47.8，35.5，

33.9，31.5, 29.8, 25.1. HRMS (LSI): m/z 686.1503 (calcd. for C31H37IN5OC11 [M]+

686.1183). Anal. Calcd. for C31H37IN5OCU • THF: C，55.44; H, 5.98; N, 9.24 %.

Found: C, 55.47; H, 6.19; N, 9.35 %.

115

Cu(HL^)I (89). This was prepared analogously to Cu(HL^)I 88，starting with HL^

(38) (0.44 g，1.0 mmol). Recrystallization from THF afforded compound 89 as

colorless crystals suitable for X-ray structural analysis. Yield: 0.13 g (22 %). M.p.:

249-250 °C. 1h NMR (DMSO-de): (5 = 13.10 (s，1 H, OH), 8.44 (s，2 H, Ar), 7.63

(m, 2 H, Ar), 7.33 (m, 4 H, Ar), 7.17 (d,J= 6.0 Hz, 1 H, Ar), 6.80 (t, J= 7.5 Hz, 1

H, Ar) , 4.02 (s，4 H，CEb)，3.91 (s，2 H, CH2), 1.38 (s，9 H，,-Bu). ^^C N M R

(DMS0-d6): (5 = 155.5, 150.2, 141.5, 135.3, 133.2，127.9，126.0，123.5，122.2,

119.3, 119.2, 112.0，67.0, 56.5, 47.8，34.3, 30.0，25.1. HRMS (LSI): m/z 502.1701

(calcd. for C27H29N5OCU [M-I]+ 502.8369). Anal. Calcd. for

C27H29IN5OCU • 4CH3OH: C，49.11; H, 5.98; N, 9.23 %. Found: C, 48.78; H, 5.45;

N，9.10 0/0.

116

4-D. Oxo-Transfer to Triphenylphosphine as Described in Chapter 3

Reactivity of [Cu(HL^)(//-!)]2 (86). Dioxygen was bubbled into a yellow solution

of[Cu(HL^)(/z-I)]2 86 (0.46 g, 0.38 mmol) in dichloromethane (15 mL) at -80 °C for

5 min. to give a deep brown solution. A slight excess of 1 equivalent of PPhs (0.10

g, 0.38 mmol) in dichloromethane (15 mL) was then added dropwise with stirring.

The solution was stirred at -80 °C for 18 hours. The resulting solution was wanned

to room temperature, and all the volatiles was removed under vacuum. The residue

was extracted with several portions of diethyl ether. GC-MS analysis of the ether

extracts showed a quantitative conversion of PPha to PhsPO.

Reactivity of [Cu(HL^)(/z-I)]2 (87). The reaction was studied under a similar

conditions and work-up procedures, starting from [Cu(HL^)( [i -I)]2 87 (0.32 g, 0.29

mmol). GC-MS analysis of the ether extracts showed a quantitative conversion of

PPhs to PhaPO.

Reactivity of [Cu(HL'')I] (88). Dioxygen was bubbled into a colorless solution of

[Cu(HL4)I] 92 (0.16 g, 0.23 mmol) in tetrahydrofliran (15 mL) at -80。C for 5 min. to

give a yellow solution. A slight excess of 1 equivalent of PPha (0.06 g, 0.24 mmol)

in tetrahydrofliran (15 mL) was added dropwise with stirring. The solution was

117

stirred at -80 °C for 18 hours. After the solution had been warmed to room

temperature, all the volatiles were removed under vacuum. The residue extracted

with diethyl ether. GC-MS analysis of the ether extracts showed the presence of

PPhs only, with no formation ofPhaPO.

118

4-E. References

1. Larsen, S.; Michelson，K.; Pedersen, E. Acta Chem. Scand A 1986, 40, 63-76.

2. Berends，H. P.; Stephan，D. W. Inorg. Chim. Acta 1984，93, 173-178.

3. Sokolowski, A.; Muller, J.; Weyheraiuller, T.; Schnepf, R.; Hilderbrand, P.;

Bothe, E.; Wieghardt, K. J. Am. Chem. Soc., 1997,119’ 8889-8900.

119

APPENDIX A H and NMR Spectra

A- l . ^H and NMR Spectra for Compounds Described in Chapter 2

A-1-1. 1h and NMR Spectra of H i / (37) 外成 — r t� m O 一�r Current Data Parameters

r. 实另�2S：：二�S� � ° - MAKE ecc033h,-d«0 ^ 2 rvr^r^h r^r^hU；� � V W tt m m m m� � EXPNO »

° — ^ v / / / I I \ \ l :。：=, t一一

"’灯「� II丨I Date. 20010109 Time 11.50 ！NSinUM dD«300 PffOBHO 5 m« Dual 13 PULPROG zg TO 32760

H SOLVENT *ceton ( N ^ ^ FI ORES 0 .274439 »Z

AO 1.9219508 sec J V-f•日 U AG 101.6 OW 55.500 usee OE 6.00 usee

/ TE 300.0 K f - B U 01 1 .00000000 s e c

CHANNEL fl NUCI IH FM 4.50 usee PLl -2.00 d8 SFOl 300.1312000 KHZ

F2 - Processing parawters SI 32768 SF 300.1300012 MHZ NOH EH SSB 0 LB 0.30 HI GB 0 PC 100

10 NMR plot paraneiers , CX 23.00 cm A I FIP 12.000 DO"

MJu iLLJ V——I_1~JUl 三 r /V\ \ / l \ z" ,二二r

. s g[ig]s] gS s 2 _ I i s sss s s CO m o I o m .r" - o -

_ .0 T 5 ^ _. ] . . . .. ° •

Current Data Parameters NAHE ecc033C-c}niso EXPNO 1

\l \\\I\W/ ^ ^ ^ ^ ^ ^ ^ ^ TO 55536 SOLVENT CDC 13 NS 837 OS 0

jj |j SWH 22675.736 Hz A n n ^ ^ FI ORES 0.346004 HZ

^ ^ ^ 0€ 6.00 usee D,, TE 300.0 K

y - ^ l - D U D, 1.00000000 s e c n U ' ^ y ^ ^ / a n 0 .03000000 s e c

i D,f …………CHANNEL f 1……• f-SU HUC1 13C

PI 3.00 usee PU -6.00 (10 SFOl 75.47451U MHZ

. . . . . . . . . . . . C H A N N E L f2 CP0PRG2 waltz 16 NUC2 )H PCP02 100.00 usee Pia 120.00 d8 PU2 19.00 as ST02 300.1315007 MHz

F2 - Processing oarameters SI 65536 Sf 75 4677BOO MHz MOW EH SSB 0 La 3.00 HZ GB 0 PC I 40

10 NMR D】ol parameters CX 23.00 cn FlP ？00 000 Otjm F1 15093.55 Hz

I I I I F2P -?0.0Q0 oon 'I . J J ... . _ 」 • 、 . ，� .� f�..�rfg� -1509-35 HZ

* 納，一 Ml•"〜（-.1.�X.，，.•”II、...11 ":「••- '•‘ -fpp ^ 9 55522 Dom/cm HZCH 7?1 86572 Hz/cm

Dpm 180 150 140 120 100 80 60 40 20 0

120

胁

ssS

ii

」一

ri

s

i

？ Errll

s

2二

ii

」s

一

一

rs邮

f

s

srrii

二 I:

J

g

i 。

，

Ii:二

ii

SJ^

r3二

=

咖

⑶

：

3

,

嫩舰•测二

Ja

w

2

80L

ow

J-

L

？

n

r

c

n

2

3

o .

wow

.w

a—

-

1

8

h

⑴

咖

丨

1

5

挪

叫

则

刚丨

2

丨

10

5

S

S

晰

7

U

I

2

5；

5

“

“

t

加

则

S

拟

1

S

叩

-

-

1 02

, I

s

嶋

舰

g

S

汗 5

M

I

咖-r咖

E

朽

™

I

M

t 呢

•SStJiSS

5

H

脚

"s

Is

-

WB

N

p

p

w

w t

蛇视 8

2

H

赃

1

“

a Is

-

w

8

N

叱

5

lo

lo

3 1

T

5

HA^MAyn^

d s

o"

/ J

f ,

y

J-

c 2-

?

「冲

ST

1

i」」

s J

g.s

」

z.

S.E、

I,

w E5-1-——

IX

mam^^

i

N

{

彳

c J

hn/^n

w/^

A

n H

“乂

o

•一

w

MVD/U

^

d 5®.HI

X

H

.6

N/vh^

一

:

.H 悬、多

a

—”⑶

2. so.^u^

HN\vn

H

rt^

八。19:

is.gsl

——

I

^

A

o

J

丁

•

si

」//

s;

」//

- L

」

们S5;

」

g

m a

»

t

i

〔

p

eaa

n

L

D

1

PP®

I，

丨0,叫

ra丨

咖

‘ Q

。彳

Q 户

丨

. R

R

. S 千

_

�

f--

^

二；二

：

^r

�fi：

：：

; ffi

^^129.104

\V7.O84

P f

—

=：12

5.876

cn

- \\V

-7.076

P

r�

.�123.504�

\V-6�73d

CI*

、123..130

[6.706

—

r 115.456

厂4�872�

^�

、丨�5.700�

⑴ O

m-

/ r 4.087

r"^^

‘:

1 p

jf

^ 3

‘ 1

|i I

r 56.3

96

> 00

°�

〉�—�

�.9.285

S

___

I;:丨丨丨

I

丨I

^^

34.67

4

W

、31.923

厂1.263�

p�r

t -21

5

—

一

^1.2

07

Q

、I.179�

V^�

o-

= °

sssgjv! 二�

=�A 丨

⑶

sssg室�ssi 旨

宝二�ss：�ssse

，„

〜，

。„

,。

” i

,…

"丨

--

j i

i H

fr-

PI

…s

i,『

！丨

…！

。|

p?

iiiiS

iP

i-.J

il

llll

M

kd

Ihii

il.i

iJk

il

y ii

i^ii

J -

。

L5

L

i

L.-

iii

..

Ij

If

Ir

--

‘ ^

‘至舌”

i

”i

丨『

y

! 一

…

Ipm

r ll

ri

—

•

•

9 2

“

u “

on

“

=

a

沖

议

£

m

【

二」-rr

s

srrli

I

=」-一

ri

一

r二

s

s

s srrll

ls"g。？ss£。二二咖g二 "Esgg

fsssosog

sggsgssig

SB丨

二二

= Sgo二§S§11

观sm

二

l

g

l

s

。

g

。

s

；咖sis^s

Ii

P>§

— SI

s

M

-

m r§

「二二二

II

pg

~

§§

i

"

!

"

I

i

pis

J

80

1

2

™

则

叫

g

们

=

™

~

丨

lo

5

e

£

咖

叫

e

邮

6

t

3

M

3

p

a

1

5

t

i

n

s

a

1

5 a

t

s

n

_

s

t

t

9

a

s

t

d

I

-

•

c

o

•

V

I

K

e

o

山

u

"

！

I

Z

I

l

o

g

"

o

a

m

o

p

州 s

y

w

例

。

•

你

阳

S

I

1

I

w

H

們

s

卿

删

=

例 m H

I

S

J

J

l

s

i

哪

-

“

9

m

p

p

raw

lo

6

nM- 5-1

mn^

Aso"

5-OE

1/

c 。浜二—-1

H

A

.

八

6

C

2

突-^

j

K 1

ss

々

:

1 2s

9£

L -2

9

二 Bt^-^

叩

n 二Z.0.

」

z 856•芝

A^ 1

-—-

」

s I

丄

口二、

沈

二二\

—

UAI

：

.g

ogvlv M

M®M

；

R 3

公 2

^ I

,——

.,5

B

⑴

I

：

XK&P

IT J

z^

-则

Q i

u

,s

”

”

？

咖

——L

% 頸I

SY

\l

:

:“：：〔

J

,H Ij

c

xft

夂

§01

—mm^

• ；Jnfr

、

1

la^

nnn^s

18

I

1

4 ^

2E0-SI

M (！”『

- S6;

」/

A eoo-e

」

-9

s JJY

i

八 goo

g

m

. i

l

uidd

【卯

i a

LP

c

c

»

c

wc

s c

e

e

c

a

e

z

z

ffi

n

A

I

c

c

•

c

>

c

A

浓 S

S

K

S

S SSJ

S

S

SS£g£g

似

们

讯

r

i 咖

s

敝

！

咖

ss

晰

,

附

5

•

r r

^

二； ss

J;⑷二•"§

J

ssosog

"gispi

i2£ISOS§is

。ss

2…ggs

…s。g

。s

sggsgE

r pnl

gSS

®

§

I

“

“

“

II

s

I

他

-J

I—

晰

⑶

^

—

1

5

咖

叫

咖

=

p时刚

「

™

。咖

S

咖

g

叫

f

C

-

'

-

«

她

m

s

棚

S

“

“

3

二“隨 IJElei略SUSSES

f

ssS〔…i

IE

imiieLsi謹Esiesi

liLi

…⑶

…」1

lo

7 o

^^ I

i

八专

d T

™

n

z se.工

6I9>E——

丄

f 2E’？

；

o 13

K srE-^

000.?

-

-

-

e—^

\

to 墨

H

二”^

1

^

i.E——

1

MMnyw

ogs

、/

s A

/i.z

仪 "二

％ ^

M i.

J

a

n

p. SB

+ r--

w u

§

a •

i

:

J.

I •

」_「7

I

卷

-

l

A

-

.

IH ")>

丄I

；

y

. i-7

t^Jj

L

1\

-so--/

M^

⑷

5 <

〜0000-g

「8

一

1

察•

L」 8t6.6M

^ j

<； 220-8」

I

i--

沒0V51

I

_叨

>9

i

1

印

i If,

【卿

i

】

LS

o 1

ppm

si

一。sg

「al

ppm

o .

w

:

w .

/-8.6s

V

SI

T

/^8.652

-

o J^

「7.g48

I

-f h

w T

‘

I 1

>

#

丨

S-

—157.…

1

V

A.要

H

；

V

^ lis

I

v.〜§

热H

g

/ \J

」Y^

v-25.089

《VL

vs.906

}

.Tl

？^cc/

^

g」

^

叩

f

HI

o \_JI

8

\-124.341

r\

n

N

w

n §

SJ

T

——4.906

c. 、4.2S

s

“

mT

小二：“

I

:IVT

二〕-

即

「61.066

^3.320

o

l「g-os T

K^

」/「-19.852 夕3.310

-_.

M

‘ —

」「49.569

El

一/「

S.2B5 \-3.2g

— J^

自-

u/

「 •二

S.717

T_

V- 48.434

/

r

I

w V

4P150

a^

-iv

飞

2.082

/(V

^Mn

— —--—

36.007

Mv 34.2B

c

^Y 32.227

^

,3P23 Tl

—一.341

2

L

M0V

n

1.181

s

_

1

丨

™

i

„

卿

咖 f

I

一

g

帅

啊

9

“

TO

Q

s

s

o

l

l

s

I

叫

SJ

1

咖

咖

仙

咖

g

l

a

n

d

！

旧

“

s 二

i

iie

«

s 9

！r二 li

二：iirj

g

e

z

s

二咖 r

二

二

HS^OCOEK

1

SKI

K

6 .o

o

1

.9

E

I n

gggy-osus!^;

^^^^

^

^ 训

盼

SSWSK 川

I

o 咖

Km w

Mres^e^^^

hk

；-SMg

进

Ks

二二二 “

！

=

二

；

2

；

二-二

二

S

I

二：二

S

S ？

rss

“「SS

E

5

D

/

3

•

3

•

3

3

B

V

W

W

2

I

a

=

3

3

a

D

&

3 们

“

„

们

J

3

“ 3

3

J

003

^ u Intel

；

XX

二 PI

1

：；

0

i

出-

「8-S8

： -

y^B.570

一 >7.963

/r

t:

I

180.630

//r，s8

\

.「

：

」

w 个

I

viii

X

则」

>

——157.114

B,

ihwn

了

^

i

「「Izd

ru.

/, A

/

\/Y>

S

J/\.

彦 H

—

i)

.

！E

:

办

则

r

M

ZK

“ ，

」

i

c

p

^

I ./yVi

⑶一“

-

c

u

j

n

^^(CH

乂；•

:

营

\-J <124.3B0

1\广5.866

JM

T I

”二？

怕

\广6.322

rv

1

：广

6.2s

M

SI

4.912

I P

9 /

V4.230

？sg/ ——

个，217

d

S-j

p」

g.l779

、「

9

/. /r

:—\^3-732

「60.593

riv

>3.321

/、59.870

议

9

一 -

=^

「49.851

1=—

"^3.310

o

o ,

49.567

\--3.304

J

j/y- S.2B3

£1

_—_

肿

V

4814B

/

^

^ /

_

UI^

〈2.102

I

o

妃—

9.25V

un

1

rs

V

！.

；^

ol

ss^ Iskii

s

=

对

二

i

j

l

" 二p

d

o

-

>

3

K-

3

0

n

£

>

K

n

•

韋

C

o

o

a

•

I'

B

o

a

j

"

s

•

u

- i

s

i

咖

o.

>

E

【

卯

sw

n

咖

赃

w

咖

i

s

'09

-

«

lislsr

〕 sorsasj

rggsss

mggs"

§n§g:!§IS。rs

二

：：胍

is

二丨SS

gorssss

sgsm"

gogisisrsisssgs

二

丨

柳

pi 二 g

. ™

S

j

I

二 ™

SSll

-rH

1

= 二二

5

I

s

1二

一

sil

-rH

3

们

似

似

w

们

则

A-2. 1h and N M R Spectra for Compounds Described in Chapter 3

A-2-1. ^H and NMR Spectra of [Cu(HL^)(M)]2 (86)

6 专浜�m� S ^ S & S S S S i m S S S S S S � £� ^ ^� Current�Data�Parameters�

S� o� oi�cn� (^r>>fN.u5iDU3tou3U5u3u3ujioioio� m� m — 二朴明� ecaoeia-ni�

“ V ^^^^^^^^ 二 ‘ I� 1 I a r r� F2�-�ACQuisition�Parameters�

Oate^� 20000325�rime� 11.12�INSTRUM� dOK300�PflOeHO� 5�am�Dual�13�PULPROG iq

f T 》� f D� TO� 32768�f -Bu l ^ J / - B " r " ' ，

c i O c u I X j i L 二 fg� ‘� fll^J� *Q 1.8219509 sec

/-Bu C H I ^ 1 iT ^ ^ ^ DH 55.SCO usee ^ 6.00 usee re 300.0 K 01 丨.00000000�sec�............CHANNEL�fl … … ， NUCl IH PI 4.50 usee

PLl� -2.00�OB�SFOl� 300�1312000�MHz�f2 -�Processing�parameters�SI� 32768�SF� 300.1300314�MHz�HOW� EM�SSB� 0�L8� 0.30�Hz�GB 0 PC 1 00 10 NHR plot Ddrameters CX 23.00 cm

I I FIP 12.000 pon I I H i 3601,56 Hi

A A n /LJULA /V A . > -O.soo pp*

A l\ A m l\ A 二。’二 - fn] fo fol fcnloi f\il / 卜、 a )� f l HZCM 163.11415 H"c« ？� u 3 o� rvj� �—.�� oj� r\j� i n c D�9� o� m m i ^ o� c\i� rn� In� ^�2� cr>� o� CT0010� OTOT� —� r\j�—� o� ru� o� f\j�ru�OJ� m� --� crioi�

I I 丨'_ I 丨• , I I t

卩 Jjm 10 9 6 4 2 0

Current�Data�Par«»eiers�NAME ecd0e]a-cl3

« ^ is SsSssgSssisS oS 5兰sg = ‘ a.� ua^v 一一� u3io®a)®r«-inTrfn<n 一 m in iri a� f?�-�ACQuisil�ion�Paraoeters�

S� S� m�n�m� Date� 20000325�

\lI \l \\l/ S r � 丨 PULPROG ,90c TO 55536 SOLVENT CDC 13 MS 2B04 OS 0

/ ： ^� SWH� 2?675�736�HI�fj� 〕� fl� FIWES� 0.346004 Hi

* D,, il ^J 11 yA u n N B U AO 1 4451188 sec

_ An N ^ V ^ I ^ -096 ^ \ „ 01 1 00000000 sec

f-Bu ^ 1] K II /-Bu on 0 03000000 sec

CHANNEL “ WXl 13C Pt 3.00 usee PU -5.00 d9 STOl 75 4745in MMr

CHANNEL r? CPOPPC? xaUi 16 MUC? ]H PCP02 100 00 usee 气2 】？0�00�OB�PL12� 19�00 OB STO?� 300�1315007�mw,�

F?�-�Processing oara*ters SI 65536 SF 75 <57 7296 mi tiOit EM

I SS9 0 La 3 00 Hi se 0 PC 1 40

ID plot oarareiers CX 23 00 cm

1 FtP 180 000 0D» } I ' ' I Pi 13564 19 H;

J L _J、i I ^ U-J� 1_y� /� LJ� L U J � F?� -1509.35�h?�

B�59555 po /c* ；� ^H^CM� 5S6 ？<109�

150� UO i?Q� 100 50� 50� 40 20� 0�

127

A-2-2. ^H and NMR Spectra of [Cu(HL^)(^-I)]2 (87)

in o o) mnj(Mioo)rv.r>.o>iDinfnf\>oj(Oi£Jfn r- in us� ①� Current�Data�Pararaeters�g� m�<M� m m n� — 卜（ C i D i n m m� cm� tn NAME� ecc084�g� d� oi�o>� •�lOioiOiOiDioiDiDtoiOifito ，� m m� —� EXPNO� j�

\ / - Acqu is i t i on Parameters

Da te . 200104!0

Time 18.46

INSTPUH dp1300

PflOBHO 5 IBM Dual 13 PULPflOG zg

^ ^ TO 32768 f ] f i ^ SOLVENT C606

r 尋 , - 「 O H V ^ ' Y H oh 55.600 usee

f - B U OE 6.00 usee

k：^^� TE� 300.0�K�01 1.00000000 sec

. . . . . . . . . . . . C H A N N E L M

NUCl IH

PI 4.50 usee

PL! -2.00 dB

SFOJ 300.1312000 mz

F2 - Processing parameters

SI 32760

SF� 300.1300322�MHz�MOM EH

SS8 0

LB 0.30 Hz

68 0

PC 1.00

10 _ p lo t paramelers

CX 23 00 cm

I J FIP 12.000 Dpm I jl jJLMi ： I , L I jj- • . F p p ^-O'mo :

A A / V A V A A A A 監：王 " rvj� o� o� r�m� �m�o>� to� o� m� m�

u� � IT)� o� oj�m�•-«�oi�ID� OT� � (D� cn�J� OT� 03� o� o�r�CM�OT�O)� n j r - m� r-c� o� —•� —�cu o r u o— 一� oo�

ppm 10 B 6 4 2 0

Current Oata Paraneters

NAME ecc084_cl3 exPNO 1

CM CD LO • ^ ' » c \ i ( \ j o a 3 n f n m m m m ru o i PflOCNO i ① （ D O o - * o a o t D m o > o o \ ^ in •»- i n i o g • rn 一 if)mr«.non<J>*J"ioin rr ” ru

g r.- oi rvj r^r^aidoir^ir^f^�� o；� cr>�ua� m o� F2�-�Acqujs.tion�Parameters� .�if> i n tn m m n j c g o j r u f v j r u o j - r ' m m m m Oate 300)0417

V I \| I I iHr 二 ? PULPflOG zgdc TO 6553B SOLVENT C0C13 NS 3693 OS 0 SHH 22575.736 H2 FIDOES 0.346004 Hz

H ii Q ^ H O /-Bu II usee "V- I ^N^^^V^ OE 5.00 usee I� .“、i、、l/""“� t� I� Te� 300.0�<�

//� C U < 1� N ^ v� //� ot� 1.00000000�

/� � � \� 《 01] 0.03000000 sec

I J ^Y H …•….•…••. PI 3.00 usee PU -6.00 dB SFOl 75.4745111 MH?

CHANNCL t2 • • • • • • , CPOPflG? » a l t r l 6 NUC2 IH PCPO? 100 00 usee PL2 IPO.OO flB PLl? 19.00 dB SF02 300 1315007 MHz

F2 ‘ Processing oarawte rs SI 65536 SF 75.^677053 MHl . HOW EM S5B 0 LB 3.00 HZ ca 0

PC 1.40

10 NHp olot D«f"a"Mters I CX 23.00 c«

FIP IBO 000 DP* n 135BM9 Hi

I I I F?P -20 000 00(»

‘ . , ^ HZCM 555 24091 Mz/Cff ODm 160 MO 120 100 80 50 -JO 20 0

128

A-2-2. ^H and NMR Spectra of [Cu(HL )( -I)]2 (87)

„ r*. T r g c v j o i r - i D Current 0«t« ParanetBrs g ti ry ^ l o i o m m m m m r u - ^ — ' o o O O T U J i n m m ^ ^ ecc071 a ^ o； a i r." r " r： r." r.' r - r - f-" f - f-' r^' ^ m m m m r ； £XPNO 1

I I WW KW// Date. 20010315

rime 13 27

INSTRUH dox300

PR06K0 5 Dual 13

NBu 舰麵 rt^rV/OH \ SOLVENT DHSO XX 0 l^QU N SHH� 8992.806 Hi

/ \ FIORES 0.27i439 Hz V C u AO 1.821950B sec / ^ M ^ TO 138

H N I 丨 OW 55.600 usee

OE 5.00 usee

TE 300.0 K

A j j 0� I.OOOOOOOO sec . . . . . . . . . . . . C H A N N E L f ! " " “ •

NUCt IH

PI 4.50 usee

PL! -2.00 dS

SFOI 300.1312000 MHz

F2 - Processing oarameters

SI 3276B

SF 300.1300015 MHZ

WW EM

ssa� 0�LB 0.30 HZ

GB 0 PC 1.00

10 _ o i o l parameters I CX 23.00 cm

丨 f IP 14.000 ppn

I A A 1 Al I JUjUl I lUul '二： . . . , , , , ,, 11 F2 -150.06 Hi

？ N 3 5 12 g g] 2 S S £ 5 m o? r o o S r- C71 ：丨二？二� o� —•� r\j� o�o� m卜� oilcn�

I�M�•� '�i�"�I�•�I�I�I�•�I�>�.�• ，,r-� '�I�"� '_..-.� I 丨� I� I�'-"�-ppm� .12� 10� 8� 6� 4� 2� 0�

Current Data Parameters

NAME� ecc014C-amso�EXPNO 1

c n — o i f - i n t D 臂 r n u j i o 卜 o o ) r«. l o o j 臂 r - » o i — n m r > « r ^ ， o j o t n PBOCNO 1 o�in� inf^ioo»f\jotDO>aocDo� —� inrviinr-cnru^LDCD-^cDOoru�

I.� -� o� pj�.� p p t rs�

SS ？ £ Date, jooioao? • n \ i \ r s \ w I = “ 。 H

pulPTOG zgdc TO 65536 SOLVENf CDC13 NS 2933 OS 0 5MH 22675.736 HZ

t P y FIOflES 0.346004 Hz I . / ^ AO 1.4451108 sec

- j ^ k ^ O H H N - \ \ y ) 呢� 9,98�r ^ if J� j i y� OH� 22.050�usee�J ^� 11� I — O E� 6.00�usee�

k O i l ISI 1 TE 300.0 K

f-D"� f� \� 01� r�00000000�sec�( C u Oi l 0.03000000 sec

UfsJ� 7 丨� ••……•…CHANNEL�fl……'�‘ 1 NUCJ 13C

P 3.00 usee

/ / / PU -6.00 dB

^ ^ ^ ！ SFOI 75.4745111 KHz

. . . . . . . . . . . . C H A N N E L f2

CP0PRG2 wa lU ie NliC3 IH PCP02 100.00 usee n.2 120.00 dB PL12 19.00 08 SF02 300.1315007 MHz

F2 - Processing parameters I SI 65536

SF 75 4677830 MHz KOK EH SSB 0 LB 3.00 HZ G8 0 PC 1,40

10 NMfl p lot parameters CX 23.00 cm FtP leo 000 00*

Fl 13584,20 Hz

U | I / F2P -20 000 ppm

HZCH 655.2415日 H"cm

Dpm� 160 ！�40� 120� 100� 80� 50� dO� 20� 0�

129

A-2-2. ^H and NMR Spectra of [Cu(HL )( -I)]2 (87)

o q*in”iD^^ru — ODiD(Mor-nj — r u o c o m m o c o l u — oCT>CDr-iD"«»ncD Current Qata Para»eie'"S p l O i D U j m m m m — 'âaajr^. o c n i o i o m m— Q NAME eCCO O Q m� a3r««r>-r»-r-«r»»r-r-•卜�r«-u3u3LD，r*"imf^nmnfnnnr\jf\jr\j 一� —�—�—� EXPNO� 】�

I 1 1 H iT ^ ! ^ 1� T [ F2 - Acquis i t ion Parameters Date. 20010319 Time 19.12 INSTRUM do*300

1 Q.. — PfiOBHO 5 im Dual 13 卜 tJU / = = \ PuLPnoG Jk OH HN—(v /) TO 32768

/ / / SOLVENT DMSO

n \ SMH 8992.806 H? ( p FIOBES 0.274439 H? k i ^ ^ ^ W 、 AO 1.8219508 sec

W M V ^ I TO 322.5 J W 55.600 usee

0£ 6.00 usee

I n TE .300.0 K

U 01 l.OOOOOOOO sec

CHANNEL f I

NUCl IH

PI 4,50 usee

PLl -2.00 06

SFOl 300. 1312000 MHz

F2 - Processing parameters

SI 32768

Sf 300.13000J0 mz

KOW EH

5Se� 0�L8 0.30 »Z

G8 0 PC I 00

to Nwn plot paratneters J CX 23 00 cn

I MP M.OOO pp.

k A JlRJ . 1,1,U . J.il P T 二 l\ i\ / \ / M / f \ A 二二二

- L ] H /OYCD ml ail |<n丨f^ c=,] H2CM 189,21239 H /cm « ‘ f\j| T (o m m oi ！ oi 丨•“』 icD ^ irv o丨 [o cn cni m 〜丨rr ir-S" ‘ — cn o cn cn cd'od o -� •!� !�-�-I�-I •！ •；� -1� I� .�三一_� I»-•‘� I�rvi��I�11�o� m'—.� I�oi�I�

ppm 12 10 a 5 4 2

Current Data Parameters

MAME ecc040j:13

EXPNO 1

rx oj — ojocTiiD 〜o 对 ruu3 o r>.-«oiiflCDofM*jiDcoioiDruai PflOCNO \ o> •^nmtotDincDrxru uinrumrôru*TiO(Oir)cncD"-*

g -T OJ If) mrvjcno'^fviryô o m c D r - - m o m i n r u c p U 3 m o i o — g i n o ^ r.' u D r - i n d d c n o i O T m a s ^ o c r i i n F 2 - Acquis i t ion Parameters

m in T m m n j o j o j C M - - — lo i n - T r r T r - T m m m f n m m f n r u r u Date 20010320

M r \ r \ \ w I = 』 • PULPTOG jgdc TO 65536 SOLVENT OMSO NS 6066 t-Bu OS 0

I SHH 22575.735 Hz ^ ^ S ^ O H H N ' ^ V y ) FI ORES 0.34&004 HZ r I f j L ^ y AO 1.4451188 sec

Ji AG 9195.3 H 1 ON 22.050 usee

/ \ OE 6.00 usee L TE 300 0 K

\ , DI J.00000000 sec HN I I dll 0.03000000 sec 丨 … … … " C H A M N E L fl

( / / NUCl 13C

PI 3.00 usee

PLl -6.00 dS

SFOl 75.4745111 MHZ

. . . . . . . . . . . .CHANNEL f2

CP0PRG2 waltzlB NUC2 IH PCP02 100.00 usee PL2 120.00 d8 PL 12 19 .00 OB SF02 300.1315007 MHz

F2 - Processing parameters St 65336 Sf 75.467784丨 MHZ

MOW� EM�SSB 0

L8 3.00 HZ

GB 0 PC 1.40

10 NHR olot parameters CX 23 00 cm MP 160.000 Dpn

I I n 13564 20 HZ . I i F2P -20 000 ODO

HZCM 655 2415B Hz/cn I •… 厂 , … ' I I I T， r - ^ - r - . ~ ~ ~ ' ••‘~I … . ~ T ‘ ― ^ ' ' ' | '“''''''' ppm 160 140 120 100 80 60 40 20 0

130

APPE

NDIX

B C

rysta

llogr

aphic

Dat

a (C

ontin

ued)

B-1. X

-ray C

rystal

Struct

ure Da

ta for

Comp

lexes

(51，52,

54 and

55) D

escrib

ed in

Chapt

er 2

~

[Cu(HL»)C

l]C

l (51)

[Cu(HL»)(

OA

c)](

OA

c) (52)[CU(L')(OAC)] (54)

[Zn(L')

Cl] (55)

Empir

ical

Form

ula

C27

H35

CI2

CUN

3OCH

2CI2

O.5

H2O

C29

H37

CUN

3O3C

H3O

H2H

2O

C^^H

^^CIN

^O

^

Form

ula

Wei

ght

645.

95

656.

75

607.2

3 517.3

9 Cry

stal

Sys

tem

m

onocl

inic

tr

iclinic

tr

iclinic

ort

horh

om

bic

Sp

ace

Gro

up

C2c

PT

PT

Pna2(l

) a/

A

34.2

25(7

) 13

.237

(4)

8.6

502(1

7)

23.2

58(5

) b/A

12

.130

⑵

13.7

21(5

) 10.0

08(2

) 13.9

73(3

)

c/A

16.6

50⑶

20.9

26(7

) 20.4

36(4

) 8.2

841(1

7)

a/。

90

96.5

8(2

) 89.8

2(3

) 90

Q/o

110.2

5(3

) 100.3

8(2

) 84.0

8(3

) 90

- 90

108.8

1(2

) 64.5

2(3

) 90

—

Volu

me

/A^

6485(2

) 3477(2

) 1586.9

(5)

2692.2

(9)

Z

8

4

2

4

Densi

ty/M

gm

-^

1.3

23

1.2

54

1.2

71

1.2

77

Abso

rption

Coef

fici

ent/

mm

'

1030

0.67

8 0.7

32

1.03

4 F(O

OO

) 26

88

1394

64

6 10

88

Cry

stal

Siz

e/m

m

0.40

x 0

.35

x 0.

05

0.2

2x0.2

0x0.1

5 0.4

0 x

0.3

6 x

0.2

4 0.5

2 x

0.3

7 x

0.2

2 Te

mper

ature

/K

293(2

) 293(2

) 293(2

) 293(2

) G R

ange

for D

ata

Colle

ctio

n/^

1.79

-25.

00

1.67

-25.

00

2.0

1-2

4.0

0 2.2

8-2

5.4

8 In

dex

Ran

ges

0^

<40, -1

3<k<

12, -

19<1<

18

-1

5^

<1

4,0

^1

6,

-24<

1<24

-9

<h<

8, -

11

^0

, -2

3<

1^

3 -2

8<

h^

8, -1

6^

0,

-9<1<

9 N

o. of Ref

lect

ions

mea

sure

d

7373

63

30

4069

7778

N

o. of In

dep

enden

t Ref

lect

ions

4517

63

30

4069

4297

Goodne

ss-o

f-fit

on

F^

1-07

7 1.

102

1.06

4 1.

044

Final

R I

ndic

es [

I>2

ct(

I)]

R

= 0

.0824，

R^ =

0.2

132

R =

0.0

828，

RW

= 0

.1961

R =

0.0

710’

RW = 0

.1934

R =

0.0

672’ R^ =

0.1

730

R In

dic

es

(all d

ata

) R =

0.0

937, Rw

= 0

.2246

R =

0.1

455, Rw

= 0

.2320

R = 0

.0763, Rw

= 0

.1988

R =

0.0

699，

R^ =

0.1

760

R�= i

|FOI-|

fJ/

i|FOI. RW

= [Iw

( I Fo I -1 F

e I )'

/Sw I Fo I

w

= 4

Fo'/A\F

o').

APPE

NDIX

B Cr

ystallo

graph

ic Data

(Cont

inued)

B-1

. X-ra

y Crys

tal Str

ucture

Data f

or Co

mplex

es (56

- 59)

Descr

ibed i

n Chap

ter 2

[Zn(L

^)C

l]

(56)

[Zn(L

^)C

l]

(57)

[Zn(L

')(O

Ac)

] (5

8)

[Zn(L

^)(

OA

c)]

(59)

Empir

ical

Form

ula

C

^^

^C

IN^

O^

OS

lS^

^O

ZK

CH

^

C29H

37N

3O3Z

112H

2O

QA

^N

AZ

i^H

^

Form

ula

Wei

ght

461.

29

546.

21

577.0

2 52

0.91

Cry

stal

Sys

tem

m

onocl

inic

m

onocl

inic

tr

iclinic

tr丄

clin

ic

Space

Gro

up

P2(l

)/c

P2(l

)/c

Pi

Pl

a/A

16.4

60(3

) 19

.976

2(19

) 9.1

389(1

8)

9.0

580(5

) b/A

12

.827

(3)

10.9

377(1

1)

11.8

57(2

) 10.4

360(6

) c/

A

17.9

21 ⑷

11.9

829(1

1)

15.1

50(3

) 15.2

577(8

)

a/。�

90�90�

90.98(3)�

95.731(1)�

3/0

144.9

6(3

) 104.7

73(2

) 104.2

2(3

) 104.3

18(1

)

—

丨。

90

90

91.56(3)

112.238(1)

^

Volu

me/A

' 2172.6

(8)

2531.6

(4)

1590.3

(5)

1263.1

(1)

Z

4

4

2

2

Densi

ty/M

gm

-^

1-4

10

1.4

33

1.2

05

1.3

70

Abso

rption

Coef

fici

ent/

mm

'

1.27

2 1.

308

0.8

10

1.01

2 F(

OO

O)

960

1128

61

2 54

8 Cry

stal

Siz

e/m

m

0.6

0 x

0.30

x 0

.20

0.6

7x0.3

4x0.1

2 0.4

2 x

0.2

7 x

0.2

4 0

.48

x0

.36

x0

.11

Tem

per

ature

/K

293⑵

293(2

) 293(2

) 293(2

)

0 R

ange f

or D

ata

Collect

ion/^

2.0

2-2

4.0

0

2.1

1-2

5.0

0

2.2

4-2

4.0

0

1.4

1-2

8.0

2

Index

Ranges

-18让

《18，

-14<

k<

14, -1

8<1<20

-23:^

<23, -ll<

k<

13, -1

4<1<14

-1

0^

9,

-13<

k<

13, 0<1<17

-1

0^

11

, -1

3^

13

, -2

0<1<18

No. of Reflections

measu

red

5458

13695

4242

8917

No. of In

dependent Reflections

3133

4446

4242

5970

Goodne

ss-o

f-fit

on

1-03

4 0.

948

1.15

8 0.9

72

Final

R I

ndic

es [

I>2ct

(I)]

R = 0

.0506, Rw

= 0

.1339

R =

0.0

375，

Rw

= 0

.0972

R =

0.0

848, Rw

= 0

.2476

R =

0.0

429，

Rw

= 0

.0927

R In

dic

es

(all d

ata

) R =

0.0

565, R^ =

0.1

391

R =

0.0

573, Rw

= 0

.1095

R =

0.0

868，

Rw

= 0

.2510

R =

0.0

673, R^ =

0.1

028

R =

E|F

OI-|

FJ/I|

FO|.

Rw =

[Sw

(|Fol

-|Fj)2

/Iw|F

o|2f

2，w

= 4

Fo2

/cj2(F

o2).

APPE

NDIX

B Cr

ystallo

graph

ic Data

(Cont

inued)

B-2

. X-ra

y Crys

tal Str

ucture

Data f

or Co

mplex

es (86

, 87, 92)

Desc

ribed

in Ch

apter

3 [C

U(H

L')(^

-I)]2

(86)

[CU

(HL'

)(H-I)

]2 (8

7) [C

U(H

L')I]

(8

8)

Empir

ical

Form

ula

C54

H70

CU2I

2N6O

22CH2C

I2

C46

H54

CU2I

2N6O

22CH2C

I2

C31H

37CU

IN5O

2TH

F.O

.5CH

3O

H

Form

ula

Wei

ght

1385

.90

1273

.68

853.8

2 Cry

stal

Sys

tem

m

onocl

inic

m

onocl

inic

tr丄

clin

ic

Space

Gro

up

C2/

c ？

IJc

PT

a/A

38.6

58(2

) 18.4

17(4

) 10.0

48(3

)

b/A

9.2999(5)

10.202(2)

12.647(4)

c/A

18.7382(10)

14.137(3)

17.739(6)

a/。

90

90

100.9

84(7

)

p/。

110.7

820(1

0)

95.7

5(3

) 95.5

01(7

)

^

y/o

90

90

101.0

78(7

)

^

Volu

me/A

' 6298.4

(6)

2642.8

(9)

2151.0

(12)

Z

8

2

2

Densi

ty/M

gm

-3

1.4

62

1.6

01

1.3

18

Abso

rption

Coef

fici

ent/

mm

-'

1-86

7 2.

218

1.26

7 F(

OO

O)

2800

12

72

881

Cry

stal

Siz

e/m

m

0.71

x 0

.65

x 0.

54

0.35

x 0

.20

x 0.

18

0.5

6 x

0.4

8 x

0.4

4 Te

mper

ature

/K

293(2

) 293(2

) 293(2

) e

Ran

ge

for D

ata

Collection/。

2.1

9-2

8.0

2

2.2

2-2

5.0

0

1.6

8-2

4.0

0

Index

Ranges

-51^

<51, -1

0仏

12, -2

4<1<24

-21<

h<

21, -1

2^

0,

0<1<16

-11血

11，

-14^

4,-

19<

1<

19

No. of Reflections

measu

red

21369

4865

5070

No. of In

dependent

Reflections

7578

4654

5052

Goodne

ss-o

f-fit

on

F^

0.9

99

1.06

6 0.9

90

Final

R I

ndic

es [

I>2

ct⑴

] R =

0.0

393，

Rw

= 0

.1120

R =

0.0

648，

Rw

= 0

.1746

R =

0.0

591,R

, = 0

.1781

R In

dic

es

(all d

ata

) R =

0.0

545’ Rw

= 0

.1194

R =

0.1

304，

R^ =

0.2

086

R =

0.0

692, R

,. =

0.1

893

R =

L|Fo

l-|F

el/Z

|Fol

. Rw

= [2

W(|F。

|-|Fc

l)2/Z

W|F。

h"2

’W =

4F。

2/CJ2(

Fo2

).

APPENDIX C GC-MS Spectra

C- l . GC-MS Spectra for Standard Samples

C-1-1. GC-MS Spectra of Pure Triphenylphosphine (top) and Pure Triphenylphosphine oxide (bottom).

丨Abundance, ~ TiCrECXD" ！ 2800000-i I 1 ！ 2 6 0 0 0 0 0 - !

I ！ j 2 4 0 0 0 0 0 j

I I 2200000

！ i j 2000000 j

1800000 i

：！

I ‘ ； 1 6 0 0 0 0 0 j

！ I

： 1 4 0 0 0 0 0 1

I 1200000] I I 1000000

i I 800000 I

！ 600000j

I 4 0 0 0 0 0 I

！ i 200000i

Time->。 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22:00 24.00 26.00 28.00

•AbJHaiK^ nC:EC2.D ‘ I 1

1 3 0 0 0 0 0 ] I 1

. ！

1200000j

(1100000 . I ！

1000000j »

9 0 0 0 0 0 ,

1

8 0 0 0 0 0 . .；

.‘� I�

‘� •� j�

7 0 0 0 0 0 ： I r ‘

i I 600000丨 I

： . I 5 0 0 0 0 0 ^ 丨

I ：；

4 0 0 0 0 0 , ：：

3 0 0 0 0 0 I

200000 *

1 0 0 0 0 0 J 丨 I

Time~> G j.OO 3.00 10.00 12.00 1.00 16.00 13.00 20.00 22.00 24.00 26.00 28,00_J

134

C-1-2. GC-MS Spectra of Pure HL^ 34 (top) and Pure HL^ 35 (bottom).

丨Abundance ""TTCTEUgTD 1 5 0 0 0 0

I 1 4 0 0 0 0

130000. l a 120000 iJ『胃

110000 Jf

100000.1 f

9 0 0 0 0 I

80000 • f •

I 7 0 0 0 0 I i f

！ 6 0 0 0 0 •

5 0 0 0 0 • I

‘ 4 0 0 0 0 J f f l F

I : 1 jj\ , j r

! 竹； V� .�.�,� . , , 1 1 1� I�

i T i r n e — > . 6 . 0 0 3 . 0 0 1 0 : 0 0 . 1 2 . 0 0 . 1 4 : 0 0 16：00 1 8 . 0 0 2 0 . 0 0 2 2 . 0 0 2 4 . 0 0 2 6 . 0 0 2 8 . 0 0

,-n—^ nCTTCnXD ~ ！

丨Abundance

110000] I ,

100000 |||fi|

9 0 0 0 0 • f '

if 80000-1 11 7 0 0 0 0 L j f

IH A/l / i _ V \ J I 4��_ I / 30000.

I 肩 iUr \

Time--> ^^^S.ho 8.00 10!00 ‘ 12： ‘ 14:00 16:00 18:00 20:00 22:00 24.00___2M9_J

135

C-2. GC-MS Spectra for the Reactions with Triphenylphosphine Described in

Chapter 3

C-2-1. GC-MS Spectra upon the reaction of [Cu(HL^)(|a-I)]2 86 with

triphenylphosphine (top), and upon the reaction of [Cu(HL XM)]2 87

with triphenylphosphine (bottom).

「Abundance rrcTEC-^D I I

； 2 0 0 0 0 0 0 ]

I

I 18000001 ‘ i ,1600000 I I I . I 14000001 I

I 1200000 i

: i

I 1000000；

1 i 800000

! 600000 I

4 0 0 0 0 0

！ 200000J

i 1 i Iq j LI . 丨 . . ；

r r i m e - 〉。， I ‘ ' s . b o ‘ a.OO • I 0 I 0 O . U.OO ‘ ‘ 1 4 ； 0 0 isloo _ 1 8 ： 0 0 2 0 ： ^ 2 2 . 0 0 _ _ ^ _ _ ^ _ _ 2 8 - 0 0

bundance HC面:CT —

i 1 5 0 0 0 0 0

！

j 1 4 0 0 0 0 0 ]

1 1 3 0 0 0 0 0 j

1200000

j 1 1 0 0 0 0 0 .

1000000 9 0 0 0 0 0

800000 I

i 7 0 0 0 0 0

600000

500000

！ 4 0 0 0 0 0

3 0 0 0 0 0

200000 i

i 100000 i V I ！� I� j,� w——^�

' ' ' 6 . 0 0 ‘ I 8 . 0 0 ‘ ‘ i o ! o Q n l o o . ‘ U I Q O " ^ W . Q q ' ^ ^ I ^ Q “ 2 2 : 0 0 2 4 : 0 0 ‘ . 2 6 ： 0 0

136

C-2-2. GC-MS Spectra upon the reaction of [Cu(HL'^)I] 88 with triphenylphosphine

(top), and the control experiment without addition of any metal complex

(bottom).

A b u n d a n c e ~ nCTEC'l 1. D ‘ 2e+07j

I 1

1.8e+07-j 1.6e+07 J

？

‘� 1�

1 1.4e+07-

‘1.2e+07 ,� I�.� 1�

] I

1e+07i !

8000000 J I . -I

： ! :6000000 J ！！

i 4000000

I I I 1�

：2000000 j

.Time-> ° ' ' ' 6.00 . ‘ 8.00 ‘ 10:00 , 12!o6 . u'.OO . ‘ 16:00 . ‘ 18:00 20:00 22:00 ‘ 24!00 26!qO 28:00

l A b u n d a n c e “ rrCTECTOTD “ 2.6e+07 2.4e+07 • 2.2e+07 2e+07

i.se+orj i

1.6e+07-1.4e+07 1.2e+Q7. 1e+07.

8000000

6000000

4000000 • 20000Q0 1

t / V - I . . . . I , .

r,me-> “ . ‘ 6.00 ‘ 3.00 10:00 12:00 u!oQ ‘ 16:00 . isloo ‘ 20!00 22.00 . 24:00 26:00 28:00

137

！

I "i i .

t�

V

^ •

I •；.

••

‘

5

\ 、

：

- 」

•

•‘

，I

[ -

r

；,•

.

：、

、 __「

)

-

：

—r�.�.�hiTiftre!?''.�

CUHK L i b r a r i e s

__illlllllll 0 D 3 f l 7 1 7 S l

Syntheses and Structures of Copper and Zinc Complexes with ...

Documents

Transcript of Syntheses and Structures of Copper and Zinc Complexes with ...