配位化学：双语版（第二版）

Chapter 1An Introduction To Coordination Chemistry1

1 1The History of Coordination Chemistry1

１ １ １The Origin of Coordination Chemistry1

1 1 2The Modern Coordination Chemistry—Werner CoordinationChemistry4

1 1 3Extending Coordination Chemistry—SupramolecularChemistry6

1 2The Key Features of Coordination Complex9

１ ２ １The Concepts of Coordination Complex9

1 2 2Classification of Ligand11

1 2 3Coordination Number and Coordination Geometry12

１ 2 4Coordinative Unsaturation15

1 2 5Primary and Secondary Coordination Sphere15

１ 3Nomenclature of Coordination Complex17

１ 4Isomerism of Coordination Complex20

１ 4 1Definition of Isomers20

１ ４ ２Structural (or Constitutional) Isomers20

１ ４ ３Stereoisomers21

1 4 4Supramolecular Isomerism23

Chapter 2The Bonding Theories of Coordination Complex25

2 1Symmetry in Chemistry—Group Theory25

2 1 1Symmetry Elements25

2 1 2Symmetry Operation26

2 1 3Molecular Point Group26

2 1 4Character Tables30

2 2Valence Bond Theory32

2 2 1Hybridization of Atomic Orbitals32

2 2 2Molecular Shapes35

2 3Crystal Field Theory37

2 3 1CFT for Octahedral Geometry37

2 3 2CFT for Tetrahedral Geometry39

2 3 3CFT for Square Planar Geometry39

2 3 4Factors Influencing the Magnitude of Δ40

2 3 5Applications of CFT40

2 4Molecular Orbital Theory42

2 4 1Molecular Orbital43

2 4 2Basic Rules of MO Theory45

2 5Intermolecular Interaction47

2 5 1Electrostatic Interactions48

2 5 2Hydrogen Bonding49

2 5 3π π Stacking50

2 5 4Van de Waals Interactions50

Chapter 3Spectroscopy of Coordination Complex52

3 1Ultraviolet and Visible Absorption Spectroscopy(UV Vis)52

3 1 1Electronic Transitions53

3 1 2Absorbing Species Containing π,σ and n Electrons53

3 1 3Electronic Absorption Spectrum of Coordination Complex55

3 2Infrared Spectroscopy and Roman Spectroscopy57

3 2 1Motion of Molecule57

3 2 2IR Spectroscopy of Coordination compound59

3 2 3The Raman Effect and Raman Scattering63

3 2 4Raman Selection Rules and Intensities65

3 2 5Polarization Effects65

3 3X ray Powder and Single Crystal Diffraction Analysis 66

3 3 1Diffraction and Bragg s Law66

3 3 2X ray Powder Diffraction Analysis67

3 3 3X ray Single Crystal Diffraction Analysis69

3 4Photoelectron Spectroscopy72

3 4 1X ray Photoelectron Spectroscopy(XPS)73

3 4 2Ultraviolet Photoelectron Spectroscopy(UPS)77

3 5Nuclear Magnetic Resonance(NMR)Spectroscopy78

3 5 1Basic Principle of NMR Spectroscopy78

3 5 2The Nuclear Absorption of Radiation in Magnetic Field79

3 5 3Chemical Shift80

3 5 4Spin Spin Coupling80

3 5 5Some Chemical Shifts in 1H and 13C NMR81

3 6Electron Paramagnetic Resonance(EPR)82

3 7Circular Dichroism(CD)82

Chapter 4The Structure and Physicochemical　Properties ofCoordination Complex84

4 1The Structures of Several Kinds of CoordinationComplexes84

4 1 1Organometallic Complex84

4 1 2Cluster88

4 1 3Macrocyclic Complex and Bioinorganic Complex89

4 1 4Supramolecular Assemblies Containing Transition MetalIons(Polynuclear

Complex)94

4 2Thermodynamic Properties95

4 2 1Thermodynamic Stability96

4 2 2Stability of Complexes97

4 2 3Calculation of Species Concentrations97

4 3Molecular Electronic Devices—Redox active CoordinationComplex98

4 3 1Concept of Molecular Electronics98

4 3 2Molecular Wires98

4 3 3Molecular Switching99

4 4Magnetic Properties of Coordination Complex100

4 4 1Magnetic States of Material101

4 4 2Interaction with an External Magnetic Field102

4 4 3Diamagnetism104

4 4 4Paramagnetism104

4 4 5Ferromagnetism, Antiferromagnetism and Ferrimagnetism104

4 4 6Magnetic Behaviour of Variation with Temperature106

4 5Photochemical Properties of Coordination Complex107

4 5 1Fundamental Properties of a Photochemical Process107

4 5 2Artificial Photosynthesis108

Chapter 5Kinetics and Mechanisms of Coordination Reactions111

5 1Introductory Survey 111

5 2Reaction Mechanisms of d block Metal Complex 112

5 2 1Associative and Dissociative Reactions113

5 2 2Measurements of Rates113

5 2 3Typical Reaction Coordinates114

5 3Substitution Reactions of Coordination Complex115

5 3 1The Three Patterns of the Reaction Mechanisms115

5 3 2Substitution of Square Planar Metal Complex115

5 3 3Substitution of Octahedral Complex118

5 3 4Isomerization Reactions120

5 4Electron Transfer Reactions of Coordination Complex121

5 4 1Outer Sphere Electron Transfer121

5 4 2Inner Sphere Electron Transfer122

5 5Mechanisms of Organometallic Reactions123

5 5 1Introduction123

5 5 2Fundamental Reaction Types124

5 5 3Kinetic Rate Laws for Oxidative Addition Reaction125

5 5 4Mechanisms of Oxidative Addition Reaction126

5 5 5Migration Reaction(“Migratory Insertions”)129

5 6Elimination Reactions132

5 6 1Hydrogen Elimination Reaction132

5 6 2Reductive Hydrogen Elimination Reaction134

5 7Homogeneous Catalysis135

5 7 1Alkene Hydrogenation136

5 7 2Monsanto Acetic Acid Synthesis138

5 7 3Hydroformylation Reaction140

第1章配位化学简介143

1 1配位化学的发展历史143

1 1 1配位化学的起源143

1 1 2现代配位化学——沃纳配位理论145

1 1 3广义配位化学——超分子化学147

1 2配合物的基本特征149

1 2 1配合物的概念149

1 2 2配体的分类151

1 2 3配位数与配位几何构型152

1 2 4不饱和配位155

1 2 5第一配位层和第二配位层155

1 3配合物的命名法156

1 4配合物的同分异构体159

1 4 1异构体的定义159

1 4 2结构异构体159

1 4 3立体异构体160

1 4 4超分子异构162

第2章配合物的化学键理论164

2 1化学中的对称性——群论164

2 1 1对称元素164

２ 1 2对称操作164

2 1 3分子点群165

2 1 4特征标表168

２ 2价键理论169

２ 2 1原子轨道的杂化170

2 2 2分子形状172

２ 3晶体场理论173

２ 3 1八面体构型的晶体场174

２ 3 2四面体构型的晶体场175

2 3 3平面正方形构型的晶体场176

２ 3 4影响晶体场分裂能(Δ）大小的因素176

２ 3 5晶体场理论的应用177

２ 4分子轨道理论178

2 4 1分子轨道179

2 4 2分子轨道理论的基本原则180

2 5分子间的相互作用182

2 5 1静电相互作用182

2 5 2氢键183

2 5 3π π堆积184

2 5 4范德华相互作用184

第3章配合物的现代分析表征方法186

3 1紫外 可见吸收光谱（UV Vis）186

3 1 1电子跃迁186

3 1 2含n、σ、π电子的物质的吸收186

3 1 3配合物的电子吸收光谱188

３ 2红外光谱与拉曼光谱190

3 2 1分子的运动类型190

3 2 2配合物的红外光谱191

3 2 3拉曼效应与拉曼散射194

3 2 4拉曼选律与强度195

3 2 5极化效应196

3 3X 射线粉末衍射和单晶衍射分析法196

3 3 1衍射和布拉格定律196

3 3 2X 射线粉末衍射分析法197

3 3 3X 射线单晶衍射分析法199

3 4光电子能谱200

3 4 1X 射线光电子能谱（XPS）201

3 4 2紫外光电子能谱(UPS)204

3 5核磁共振波谱205

3 5 1NMR的基本原理205

3 5 2磁场中原子核对辐射的吸收206

3 5 3化学位移207

3 5 4自旋 自旋偶合207

3 5 5一些1H和13C NMR谱图中的化学位移207

3 6电子顺磁共振（EPR）208

3 7圆二色谱（CD）209

第４章配合物的结构和性质210

４ １几种类型的配合物的结构210

4 1 1金属有机化合物210

4 1 2簇合物213

4 1 3大环配合物215

4 1 4含有过渡金属离子的超分子自组装（多核配合物）219

4 2配合物的热力学性质220

4 2 1热力学稳定性220

4 2 2配合物的稳定性221

4 2 3有关物种浓度的计算221

4 3分子电子器件——氧化还原活性配合物222

4 3 1分子电子学的概念222

4 3 2分子导线222

4 3 3分子开关223

4 4配合物的磁学性质224

4 4 1物质的磁状态225

4 4 2与外磁场的相互作用225

4 4 3抗磁性227

4 4 4顺磁性227

4 4 5铁磁性、反铁磁性和亚铁磁性227

4 4 6随温度变化的磁行为228

4 5配合物的光化学性质229

4 5 1光化学过程的基本性质229

4 5 2人工光合作用230

第5章配位反应的动力学和机理233

5 1简介233

5 2d区金属配合物的反应机理234

5 2 1缔合和离解反应234

5 2 2反应速率的测量234

5 2 3典型的反应进程坐标235

5 3配合物的取代反应236

5 3 1反应机理的三种模式236

5 3 2平面正方形金属配合物的取代237

5 3 3八面体配合物的取代239

5 3 4异构化反应240

5 4配合物的电子转移反应241

5 4 1外层电子转移242

5 4 2内层电子转移242

5 5金属有机反应机理243

5 5 1简介243

5 5 2基本反应类型244

5 5 3氧化加成反应的动力学速率公式245

5 5 4氧化加成反应的机理246

5 5 5迁移反应（“迁移插入”） 248

5 6消除反应252

5 6 1氢的消除反应252

5 6 2还原脱氢反应253

5 7均相催化255

5 7 1烯烃加氢256

5 7 2Monsanto醋酸合成257

5 7 3酰氢化反应259

参考文献262