Introduction to coordination chemistry【2025|PDF|Epub|mobi|kindle电子书版本百度云盘下载】

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1 The Central Atom1

1.1 Key Concepts in Coordination Chemistry1

1.2 A Who’s Who of Metal Ions4

1.2.1 Commoners and ‘Uncommoners5

1.2.2 Redefining Commoners7

1.3 Metals in Molecules9

1.3.1 Metals in the Natural World10

1.3.2 Metals in Contrived Environments11

1.3.3 Natural or Made-to-Measure Complexes12

1.4 The Road Ahead13

Concept Keys14

Further Reading14

2 Ligands15

2.1 Membership：Being a Ligand15

2.1.1 What Makes a Ligand？15

2.1.2 Making Attachments - Coordination16

2.1.3 Putting the Bite on Metals - Chelation17

2.1.4 Do I Look Big on That？- Chelate Ring Size22

2.1.5 Different Tribes - Donor Group Variation23

2.1.6 Ligands with More Bite - Denticity24

2.2 Monodentate Ligands - The Simple Type26

2.2.1 Basic Binders26

2.2.2 Amines Ain’t Ammines - Ligand Families27

2.2.3 Meeting More Metals - Bridging Ligands27

2.3 Greed is Good - Polydentate Ligands29

2.3.1 The Simple Chelate29

2.3.2 More Teeth，Stronger Bite - Polydentates31

2.3.3 Many-Armed Monsters - Introducing Ligand Shape32

2.4 Polynucleating Species - Molecular Bigamists33

2.4.1 When One is Not Enough33

2.4.2 Vive la Difference - Mixed-metal Complexation34

2.4.3 Supersized - Binding to Macromolecules36

2.5 A Separate Race - Organometallic Species36

Concept Keys38

Further Reading39

3 Complexes41

3.1 The Central Metal Ion41

3.2 Metal-Ligand Marriage42

3.2.1 The Coordinate Bond42

3.2.2 The Foundation of Coordination Chemistry42

3.2.3 Complex Shape - Not Just Any Which Way45

3.3 Holding On - The Nature of Bonding in Metal Complexes49

3.3.1 An Ionic Bonding Model - Introducing Crystal Field Theory53

3.3.2 A Covalent Bonding Model - Embracing Molecular Orbital Theory57

3.3.3 Ligand Field Theory - Making Compromises62

3.3.4 Bonding Models Extended63

3.4 Coupling - Polymetallic Complexes73

3.5 Making Choices75

3.5.1 Selectivity - Of all the Molecules in all the World，Why This One？75

3.5.2 Preferences - Do You Like What I Like？75

3.5.3 Complex Lifetimes - Together，Forever？77

3.6 Complexation Consequences80

Concept Keys81

Further Reading82

4 Shape83

4.1 Getting in Shape83

4.2 Forms of Complex Life - Coordination Number and Shape86

4.2.1 One Coordination （ML）86

4.2.2 Two Coordination （ML2）87

4.2.3 Three Coordination （ML3）88

4.2.4 Four Coordination （ML4）89

4.2.5 Five Coordination （ML5）93

4.2.6 Six Coordination （ML6）96

4.2.7 Higher Coordination Numbers （ML7 to ML9）98

4.3 Influencing Shape101

4.3.1 Metallic Genetics - Metal Ion Influences101

4.3.2 Moulding a Relationship - Ligand Influences103

4.3.3 Chameleon Complexes105

4.4 Isomerism - Real 3D Effects105

4.4.1 Introducing Stereoisomers106

4.4.2 Constitutional （Structural） Isomerism106

4.4.3 Stereoisomerism：in Place - Positional Isomers； in Space - Optical Isomers109

4.4.4 What’s Best？- Isomer Preferences113

4.5 Sophisticated Shapes115

4.5.1 Compounds of Polydentate Ligands116

4.5.2 Encapsulation Compounds117

4.5.3 Host-Guest Molecular Assemblies121

4.6 Defining Shape123

Concept Keys123

Further Reading124

5 Stability125

5.1 The Makings of a Stable Relationship125

5.1.1 Bedded Down - Thermodynamic Stability125

5.1.2 Factors Influencing Stability of Metal Complexes127

5.1.3 Overall Stability Constants138

5.1.4 Undergoing Change - Kinetic Stability141

5.2 Complexation - Will It Last？143

5.2.1 Thermodynamic and Kinetic Stability143

5.2.2 Kinetic Rate Constants144

5.2.3 Lability and Inertness in Octahedral Complexes145

5.3 Reactions146

5.3.1 A New Partner - Substitution147

5.3.2 A New Body - Stereochemical Change155

5.3.3 A New Face - Oxidation-Reduction160

5.3.4 A New Suit - Ligand-centred Reactions169

Concept Keys170

Further Reading170

6 Synthesis173

6.1 Molecular Creation - Ways to Make Complexes173

6.2 Core Metal Chemistry - Periodic Table Influences173

6.2.1 s Block：Alkali and Alkaline Earth Metals173

6.2.2 p Block：Main Group Metals174

6.2.3 d Block：Transition Metals175

6.2.4 f Block：Inner Transition Metals （Lanthanoids and Actinoids）176

6.2.5 Beyond Natural Elements178

6.3 Reactions Involving the Coordination Shell179

6.3.1 Ligand Substitution Reactions in Aqueous Solution179

6.3.2 Substitution Reactions in Nonaqueous Solvents184

6.3.3 Substitution Reactions without using a Solvent186

6.3.4 Chiral Complexes189

6.3.5 Catalysed Reactions190

6.4 Reactions Involving the Metal Oxidation State190

6.5 Reactions Involving Coordinated Ligands194

6.5.1 Metal-directed Reactions194

6.5.2 Reactions of Coordinated Ligands197

6.6 Organometallic Synthesis203

Concept Keys206

Further Reading207

7 Properties209

7.1 Finding Ways to Make Complexes Talk - Investigative Methods209

7.2 Getting Physical - Methods and Outcomes210

7.3 Probing the Life of Complexes - Using Physical Methods214

7.3.1 Peak Performance - Illustrating Selected Physical Methods216

7.3.2 Pretty in Red？- Colour and the Spectrochemical Series220

7.3.3 A Magnetic Personality？- Paramagnetism and Diamagnetism223

7.3.4 Ligand Field Stabilization225

Concept Keys227

Further Reading227

8 A Complex Life229

8.1 Life’s a Metal Ion229

8.1.1 Biological Ligands229

8.1.2 Metal Ions in Biology231

8.1.3 Classes of Metallobiomolecules233

8.2 Metalloproteins and Metalloenzymes233

8.2.1 Iron-containing Biomolecules234

8.2.2 Copper-containing Biomolecules240

8.2.3 Zinc-containing Biomolecules242

8.2.4 Other Metal-containing Biomolecules243

8.2.5 Mixed-Metal Proteins244

8.3 Doing What Comes Unnaturally - Synthetic Biomolecules245

8.4 A Laboratory-free Approach - In Silico Prediction247

Concept Keys249

Further Reading250

9 Complexes and Commerce251

9.1 Kill or Cure？- Complexes as Drugs251

9.1.1 Introducing Metallodrugs252

9.1.2 Anticancer Drugs252

9.1.3 Other Metallodrugs255

9.2 How Much？- Analysing with Complexes256

9.2.1 Fluoroimmunoassay256

9.2.2 Fluoroionophores258

9.3 Profiting from Complexation259

9.3.1 Metal Extraction259

9.3.2 Industrial Roles for Ligands and Coordination Complexes261

9.4 Being Green263

9.4.1 Complexation in Remediation264

9.4.2 Better Ways to Synthesize Fine Organic Chemicals264

9.5 Complex Futures264

9.5.1 Taking Stock265

9.5.2 Crystal Ball Gazing265

Concept Keys266

Further Reading266

Appendix A：Nomenclature269

Appendix B：Molecular Symmetry：The Point Group277

Index283