Introduction to Coordination Chemistry (Inorganic Chemistry: A Textbook Series)

Introduction to Coordination Chemistry......Page 4
Contents......Page 8
Preface......Page 12
Preamble......Page 14
1.1 Key Concepts in Coordination Chemistry......Page 18
1.2 A Who’s Who of Metal Ions......Page 21
1.2.1 Commoners and ‘Uncommoners’......Page 22
1.2.2 Redefining Commoners......Page 24
1.3 Metals in Molecules......Page 26
1.3.1 Metals in the Natural World......Page 27
1.3.2 Metals in Contrived Environments......Page 28
1.3.3 Natural or Made-to-Measure Complexes......Page 29
1.4 The Road Ahead......Page 30
Further Reading......Page 31
2.1.1 What Makes a Ligand?......Page 32
2.1.2 Making Attachments – Coordination......Page 33
2.1.3 Putting the Bite on Metals – Chelation......Page 34
2.1.4 Do I Look Big on That? – Chelate Ring Size......Page 39
2.1.5 Different Tribes – Donor Group Variation......Page 40
2.1.6 Ligands with More Bite – Denticity......Page 41
2.2.1 Basic Binders......Page 43
2.2.3 Meeting More Metals – Bridging Ligands......Page 44
2.3.1 The Simple Chelate......Page 46
2.3.2 More Teeth, Stronger Bite – Polydentates......Page 48
2.3.3 Many-Armed Monsters – Introducing Ligand Shape......Page 49
2.4.1 When One is Not Enough......Page 50
2.4.2 Vive la Difference – Mixed-metal Complexation......Page 51
2.5 A Separate Race – Organometallic Species......Page 53
Concept Keys......Page 55
Further Reading......Page 56
3.1 The Central Metal Ion......Page 58
3.2.2 The Foundation of Coordination Chemistry......Page 59
3.2.3 Complex Shape – Not Just Any Which Way......Page 62
3.3 Holding On – The Nature of Bonding in Metal Complexes......Page 66
3.3.1 An Ionic Bonding Model – Introducing Crystal Field Theory......Page 70
3.3.2 A Covalent Bonding Model – Embracing Molecular Orbital Theory......Page 74
3.3.3 Ligand Field Theory – Making Compromises......Page 79
3.3.4 Bonding Models Extended......Page 80
3.4 Coupling – Polymetallic Complexes......Page 90
3.5.2 Preferences – Do You Like What I Like?......Page 92
3.5.3 Complex Lifetimes – Together, Forever?......Page 94
3.6 Complexation Consequences......Page 97
Concept Keys......Page 98
Further Reading......Page 99
4.1 Getting in Shape......Page 100
4.2.1 One Coordination (ML)......Page 103
4.2.2 Two Coordination (ML2)......Page 104
4.2.3 Three Coordination (ML3)......Page 105
4.2.4 Four Coordination (ML4)......Page 106
4.2.5 Five Coordination (ML5)......Page 110
4.2.6 Six Coordination (ML6)......Page 113
4.2.7 Higher Coordination Numbers (ML7 to ML9)......Page 115
4.3.1 Metallic Genetics – Metal Ion Influences......Page 118
4.3.2 Moulding a Relationship – Ligand Influences......Page 120
4.4 Isomerism – Real 3D Effects......Page 122
4.4.2 Constitutional (Structural) Isomerism......Page 123
4.4.3 Stereoisomerism: in Place – Positional Isomers; in Space – Optical Isomers......Page 126
4.4.4 What’s Best? – Isomer Preferences......Page 130
4.5 Sophisticated Shapes......Page 132
4.5.1 Compounds of Polydentate Ligands......Page 133
4.5.2 Encapsulation Compounds......Page 134
4.5.3 Host–Guest Molecular Assemblies......Page 138
Concept Keys......Page 140
Further Reading......Page 141
5.1.1 Bedded Down – Thermodynamic Stability......Page 142
5.1.2 Factors Influencing Stability of Metal Complexes......Page 144
5.1.3 Overall Stability Constants......Page 155
5.1.4 Undergoing Change – Kinetic Stability......Page 158
5.2.1 Thermodynamic and Kinetic Stability......Page 160
5.2.2 Kinetic Rate Constants......Page 161
5.2.3 Lability and Inertness in Octahedral Complexes......Page 162
5.3 Reactions......Page 163
5.3.1 A New Partner – Substitution......Page 164
5.3.2 A New Body – Stereochemical Change......Page 172
5.3.3 A New Face – Oxidation–Reduction......Page 177
5.3.4 A New Suit – Ligand-centred Reactions......Page 186
Further Reading......Page 187
6.2.1 s Block: Alkali and Alkaline Earth Metals......Page 190
6.2.2 p Block: Main Group Metals......Page 191
6.2.3 d Block: Transition Metals......Page 192
6.2.4 f Block: Inner Transition Metals (Lanthanoids and Actinoids)......Page 193
6.2.5 Beyond Natural Elements......Page 195
6.3.1 Ligand Substitution Reactions in Aqueous Solution......Page 196
6.3.2 Substitution Reactions in Nonaqueous Solvents......Page 201
6.3.3 Substitution Reactions without using a Solvent......Page 203
6.3.4 Chiral Complexes......Page 206
6.4 Reactions Involving the Metal Oxidation State......Page 207
6.5.1 Metal-directed Reactions......Page 211
6.5.2 Reactions of Coordinated Ligands......Page 214
6.6 Organometallic Synthesis......Page 220
Concept Keys......Page 223
Further Reading......Page 224
7.1 Finding Ways to Make Complexes Talk – Investigative Methods......Page 226
7.2 Getting Physical – Methods and Outcomes......Page 227
7.3 Probing the Life of Complexes – Using Physical Methods......Page 231
7.3.1 Peak Performance – Illustrating Selected Physical Methods......Page 233
7.3.2 Pretty in Red? – Colour and the Spectrochemical Series......Page 237
7.3.3 A Magnetic Personality? – Paramagnetism and Diamagnetism......Page 240
7.3.4 Ligand Field Stabilization......Page 242
Further Reading......Page 244
8.1.1 Biological Ligands......Page 246
8.1.2 Metal Ions in Biology......Page 248
8.2 Metalloproteins and Metalloenzymes......Page 250
8.2.1 Iron-containing Biomolecules......Page 251
8.2.2 Copper-containing Biomolecules......Page 257
8.2.3 Zinc-containing Biomolecules......Page 259
8.2.4 Other Metal-containing Biomolecules......Page 260
8.2.5 Mixed-Metal Proteins......Page 261
8.3 Doing What Comes Unnaturally – Synthetic Biomolecules......Page 262
8.4 A Laboratory-free Approach – In Silico Prediction......Page 264
Concept Keys......Page 266
Further Reading......Page 267
9.1 Kill or Cure? – Complexes as Drugs......Page 268
9.1.2 Anticancer Drugs......Page 269
9.1.3 Other Metallodrugs......Page 272
9.2.1 Fluoroimmunoassay......Page 273
9.2.2 Fluoroionophores......Page 275
9.3.1 Metal Extraction......Page 276
9.3.2 Industrial Roles for Ligands and Coordination Complexes......Page 278
9.4 Being Green......Page 280
9.5 Complex Futures......Page 281
9.5.2 Crystal Ball Gazing......Page 282
Further Reading......Page 283
Appendix A: Nomenclature......Page 286
Appendix B: Molecular Symmetry: The Point Group......Page 294
Index......Page 300