配位化學(xué)：雙語(yǔ)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章配位化學(xué)簡(jiǎn)介143
1 1配位化學(xué)的發(fā)展歷史143
1 1 1配位化學(xué)的起源143
1 1 2現(xiàn)代配位化學(xué)——沃納配位理論145
1 1 3廣義配位化學(xué)——超分子化學(xué)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配體的分類(lèi)151
1 2 3配位數(shù)與配位幾何構(gòu)型152
1 2 4不飽和配位155
1 2 5第一配位層和第二配位層155
1 3配合物的命名法156
1 4配合物的同分異構(gòu)體159
1 4 1異構(gòu)體的定義159
1 4 2結(jié)構(gòu)異構(gòu)體159
1 4 3立體異構(gòu)體160
1 4 4超分子異構(gòu)162
第2章配合物的化學(xué)鍵理論164
2 1化學(xué)中的對(duì)稱(chēng)性——群論164
2 1 1對(duì)稱(chēng)元素164
２ 1 2對(duì)稱(chēng)操作164
2 1 3分子點(diǎn)群165
2 1 4特征標(biāo)表168
２ 2價(jià)鍵理論169
２ 2 1原子軌道的雜化170
2 2 2分子形狀172
２ 3晶體場(chǎng)理論173
２ 3 1八面體構(gòu)型的晶體場(chǎng)174
２ 3 2四面體構(gòu)型的晶體場(chǎng)175
2 3 3平面正方形構(gòu)型的晶體場(chǎng)176
２ 3 4影響晶體場(chǎng)分裂能(Δ）大小的因素176
２ 3 5晶體場(chǎng)理論的應(yīng)用177
２ 4分子軌道理論178
2 4 1分子軌道179
2 4 2分子軌道理論的基本原則180
2 5分子間的相互作用182
2 5 1靜電相互作用182
2 5 2氫鍵183
2 5 3π π堆積184
2 5 4范德華相互作用184
第3章配合物的現(xiàn)代分析表征方法186
3 1紫外 可見(jiàn)吸收光譜（UV Vis）186
3 1 1電子躍遷186
3 1 2含n、σ、π電子的物質(zhì)的吸收186
3 1 3配合物的電子吸收光譜188
３ 2紅外光譜與拉曼光譜190
3 2 1分子的運(yùn)動(dòng)類(lèi)型190
3 2 2配合物的紅外光譜191
3 2 3拉曼效應(yīng)與拉曼散射194
3 2 4拉曼選律與強(qiáng)度195
3 2 5極化效應(yīng)196
3 3X 射線粉末衍射和單晶衍射分析法196
3 3 1衍射和布拉格定律196
3 3 2X 射線粉末衍射分析法197
3 3 3X 射線單晶衍射分析法199
3 4光電子能譜200
3 4 1X 射線光電子能譜（XPS）201
3 4 2紫外光電子能譜(UPS)204
3 5核磁共振波譜205
3 5 1NMR的基本原理205
3 5 2磁場(chǎng)中原子核對(duì)輻射的吸收206
3 5 3化學(xué)位移207
3 5 4自旋 自旋偶合207
3 5 5一些1H和13C NMR譜圖中的化學(xué)位移207
3 6電子順磁共振（EPR）208
3 7圓二色譜（CD）209
第４章配合物的結(jié)構(gòu)和性質(zhì)210
４ １幾種類(lèi)型的配合物的結(jié)構(gòu)210
4 1 1金屬有機(jī)化合物210
4 1 2簇合物213
4 1 3大環(huán)配合物215
4 1 4含有過(guò)渡金屬離子的超分子自組裝（多核配合物）219
4 2配合物的熱力學(xué)性質(zhì)220
4 2 1熱力學(xué)穩(wěn)定性220
4 2 2配合物的穩(wěn)定性221
4 2 3有關(guān)物種濃度的計(jì)算221
4 3分子電子器件——氧化還原活性配合物222
4 3 1分子電子學(xué)的概念222
4 3 2分子導(dǎo)線222
4 3 3分子開(kāi)關(guān)223
4 4配合物的磁學(xué)性質(zhì)224
4 4 1物質(zhì)的磁狀態(tài)225
4 4 2與外磁場(chǎng)的相互作用225
4 4 3抗磁性227
4 4 4順磁性227
4 4 5鐵磁性、反鐵磁性和亞鐵磁性227
4 4 6隨溫度變化的磁行為228
4 5配合物的光化學(xué)性質(zhì)229
4 5 1光化學(xué)過(guò)程的基本性質(zhì)229
4 5 2人工光合作用230
第5章配位反應(yīng)的動(dòng)力學(xué)和機(jī)理233
5 1簡(jiǎn)介233
5 2d區(qū)金屬配合物的反應(yīng)機(jī)理234
5 2 1締合和離解反應(yīng)234
5 2 2反應(yīng)速率的測(cè)量234
5 2 3典型的反應(yīng)進(jìn)程坐標(biāo)235
5 3配合物的取代反應(yīng)236
5 3 1反應(yīng)機(jī)理的三種模式236
5 3 2平面正方形金屬配合物的取代237
5 3 3八面體配合物的取代239
5 3 4異構(gòu)化反應(yīng)240
5 4配合物的電子轉(zhuǎn)移反應(yīng)241
5 4 1外層電子轉(zhuǎn)移242
5 4 2內(nèi)層電子轉(zhuǎn)移242
5 5金屬有機(jī)反應(yīng)機(jī)理243
5 5 1簡(jiǎn)介243
5 5 2基本反應(yīng)類(lèi)型244
5 5 3氧化加成反應(yīng)的動(dòng)力學(xué)速率公式245
5 5 4氧化加成反應(yīng)的機(jī)理246
5 5 5遷移反應(yīng)（“遷移插入”） 248
5 6消除反應(yīng)252
5 6 1氫的消除反應(yīng)252
5 6 2還原脫氫反應(yīng)253
5 7均相催化255
5 7 1烯烴加氫256
5 7 2Monsanto醋酸合成257
5 7 3酰氫化反應(yīng)259
參考文獻(xiàn)262