Comprehensive Coordination Chemistry: Theory and Background

Volume 1: Theory & Background......Page 4
Contents......Page 6
Preface......Page 8
Contributors to Volume 1......Page 10
Contents of All Volumes......Page 12
1.1.1 INTRODUCTION......Page 16
1.1.2 SOME HISTORICALLY SIGNIFICANT COORDINATION COMPOUNDS......Page 17
1.1.3 EARLY THEORIES OF COORDINATION COMPOUNDS......Page 19
1.1.4 THE COORDINATION THEORY AND THE WERNER-JORGENSEN CONTROVERSY......Page 21
1.1.5 TWENTIETH-CENTURY DEVELOPMENTS......Page 28
1.1.6 REFERENCES......Page 33
1.2.1 INTRODUCTION......Page 36
1.2.2 SYNTHESIS......Page 37
1.2.3 STRUCTURE......Page 38
1.2.5 ISOMERISM......Page 39
1.2.7 NON-AQUEOUS SOLVENTS......Page 41
1.2.8 APPLICATIONS......Page 43
1.2.9 REFERENCES......Page 44
2 Coordination Numbers and Geometries......Page 46
2.1 VALENCE SHELL ELECTRON PAIR REPULSION THEORY......Page 47
2.2 FIVE-COORDINATE COMPOUNDS......Page 54
2.3 SIX-COORDINATE COMPOUNDS......Page 64
2.4 SEVEN-COORDINATE COMPOUNDS......Page 84
2.5 EIGHT-COORDINATE COMPOUNDS......Page 98
2.6 NINE-COORDINATE COMPOUNDS......Page 110
2.7 TEN-COORDINATE COMPOUNDS......Page 113
2.9 TWELVE-COORDINATE COMPOUNDS......Page 114
2.10 REFERENCES......Page 116
3.1 INTRODUCTION......Page 124
3.2 LIGANDS......Page 126
3.3 MONONUCLEAR COMPLEXES......Page 135
3.4 POLYNUCLEAR COORDINATION COMPOUNDS......Page 137
3.5 COORDINATION POLYMERS......Page 140
3.6 METALLOCENES (BIS(eta5-CYCLOPENTADIENYL) COMPOUNDS)......Page 141
3.8 STEREOCHEMISTRY......Page 142
3.9 REFERENCES......Page 148
4 Clusters and Cages......Page 150
4.1 INTRODUCTION......Page 152
4.2 POLYHEDRA, PATTERNS AND PROGRESSIONS......Page 153
4.3 TRIMETALLIC COMPLEXES......Page 157
4.4 TETRAMETALLIC COMPLEXES......Page 161
4.5 PENTAMETALLIC COMPLEXES......Page 169
4.6 HEXAMETALLIC COMPLEXES......Page 171
4.7 HEPTAMETALLIC COMPLEXES......Page 176
4.8 OCTAMETALLIC COMPLEXES......Page 177
4.9 M9 COMPLEXES......Page 179
4.10 M10 COMPLEXES......Page 181
4.11 M11, M12, M13 AND M14 COMPLEXES......Page 182
4.12 METAL-METAL BONDED CLUSTERS OF Rh, Pt, Ag, Au AND Hg......Page 184
4.13 SYNTHESIS......Page 186
4.14 REFERENCES......Page 187
5.1 INTRODUCTION......Page 194
5.2 CONSTITUTIONAL ISOMERISM......Page 197
5.3 CONFIGURATIONAL ISOMERISM (STEREOISOMERISM)......Page 203
5.4 CONCLUDING REMARKS......Page 222
5.5 REFERENCES......Page 223
6 Ligand Field Theory......Page 228
6.1 OVERVIEW......Page 229
6.2 LIGAND FIELD THEORIES......Page 230
6.3 ATOMIC SPECTROSCOPY......Page 246
6.4 FREE-ION TERMS IN LIGAND FIELDS......Page 250
6.5 UV-VISIBLE SPECTRA OF COMPLEXES......Page 258
6.6 MAGNETIC PROPERTIES OF COMPLEXES......Page 271
6.7 MAGNETIC BEHAVIOUR OF SOME COMPLEXES......Page 286
6.8 APPENDIXES......Page 290
6.9 REFERENCES......Page 291
7.1 Substitution Reactions......Page 296
7.1.1 INTRODUCTION AND DEFINITIONS......Page 297
7.1.2 KINETICS AND MECHANISM OF SOLVENT EXCHANGE......Page 298
7.1.3 SUBSTITUTION REACTIONS IN NON-INTERFERING SOLVENTS......Page 300
7.1.4 THE SOLVOLYTIC REACTION......Page 305
7.1.5 BASE CATALYZED SOLVOLYSIS AND SUBSTITUTION......Page 315
7.1.6 COMPLEX FORMATION AND ANATION......Page 322
7.1.7 SUBSTITUTION IN FOUR-COORDINATE PLANAR d8 METAL COMPLEXES......Page 326
7.1.8 REFERENCES......Page 337
7.2.1 INTRODUCTION......Page 346
7.2.2 SELF-EXCHANGE REACTIONS......Page 350
7.2.3 FACTORS AFFECTING OUTER-SPHERE REACTIVITY......Page 352
7.2.4 THEORIES OF ELECTRON TRANSFER......Page 355
7.2.5 RATE CONSTANT EXPRESSIONS FOR ELECTRON TRANSFER......Page 360
7.2.6 ACCOUNTING FOR SELF-EXCHANGE RATE CONSTANTS......Page 362
7.2.7 OUTER-SPHERE ELECTRON TRANSFER REACTIONS WITH DeltaG # 0: CROSS REACTIONS......Page 368
7.2.8 THE INVERTED REGION: EXCITED STATE DECAY......Page 372
7.2.9 INNER-SPHERE REACTIONS......Page 374
7.2.10 REFERENCES......Page 395
7.3.1 INTRODUCTION......Page 400
7.3.2 EXCITED STATES AND EXCITED STATE PROCESSES......Page 402
7.3.3 PHOTOCHEMICAL REACTIONS OF COORDINATION COMPOUNDS......Page 412
7.3.4 APPLICATIONS OF PHOTOCHEMICAL REACTIONS OF COORDINATION COMPOUNDS......Page 423
7.3.5 ADDENDUM......Page 425
7.3.6 REFERENCES......Page 426
7.4.1 INTRODUCTION......Page 430
7.4.2 NON-CHELATE RING-FORMING REACTIONS......Page 431
7.4.3 CHELATE RING-FORMING REACTIONS......Page 448
7.4.4 CHELATE RING-MODIFYING REACTIONS......Page 469
7.4.5 REFERENCES......Page 473
7.5.2 GENERAL CHARACTERISTICS OF SOLID-STATE REACTIONS......Page 478
7.5.3 LINKAGE ISOMERIZATION......Page 480
7.5.4 RACEMIZATIONS......Page 481
7.5.5 CIS-TRANS ISOMERIZATION......Page 482
7.5.6 LIGAND EXCHANGE AND ANATION......Page 483
7.5.8 PHOTOCHEMICAL REACTIONS......Page 485
7.5.10 REFERENCES......Page 486
8.1.2 CYCLIC VOLTAMMETRY......Page 490
8.1.4 SYNTHESIS......Page 491
8.1.5 REFERENCES......Page 492
8.2.1 WATER AS AN ELECTROCHEMICAL SOLVENT......Page 494
8.2.2 OBTAINING ELECTROCHEMICAL INFORMATION IN PRACTICE......Page 496
8.2.3 FACTORS AFFECTING THE REDOX POTENTIAL E0......Page 498
8.2.4 ELECTROCHEMISTRY OF COMPLEXES CONTAINING MORE THAN ONE REDOX CENTRE......Page 500
8.2.5 MODIFIED ELECTRODES......Page 502
8.2.6 REDOX PROPERTIES OF SPECIES IN EXCITED ELECTRONIC STATES......Page 504
8.2.7 REFERENCES......Page 506
8.3.2 SINGLE ELECTRON-TRANSFER REACTIONS, ELECTRON-TRANSFER SERIES AND LINKED REDOX CENTRES......Page 508
8.3.3 REDOX POTENTIALS AND STRUCTURE......Page 511
8.3.4 CHEMISTRY FOLLOWING SlNGLE ELECTRON TRANSFER......Page 514
8.3.5 REFERENCES......Page 515
9.1 THE SOLVENT EFFECT AND RATES OF REACTIONS......Page 518
9.2 THE EFFECT OF SOLVENT ON REDOX POTENTIALS......Page 525
9.3 THE EFFECT OF SOLVENT ON EQUILIBRIUM CONSTANTS......Page 530
9.4 REFERENCES......Page 533
10 Applications in Analysis......Page 536
10.1 INTRODUCTION......Page 537
10.2 GRAVIMETRY......Page 539
10.3 MASKING......Page 550
10.4 LIQUID-LIQUID EXTRACTION......Page 553
10.5 ABSORPTIOMETRY......Page 564
10.6 TITRIMETRIC ANALYSIS......Page 567
10.7 OTHER ANALYTICAL APPLICATIONS OF COORDINATION COMPOUNDS......Page 573
10.8 REFERENCES......Page 576
Subject Index......Page 580
Formula Index......Page 606