Acknowledgment .................................................. x
List of Abbreviations .......................................... xi
1 Introduction ................................................. 1
1.1 Why Study Organometallic Chemistry? ..................... 1
1.2 Coordination Chemistry .................................. 2
1.3 Werner Complexes ........................................ 3
1.4 The Trans Effect ........................................ 7
1.5 Soft versus Hard Ligands ................................ 8
1.6 The Crystal Field ....................................... 9
1.7 The Ligand Field ....................................... 16
1.8 Back Bonding ........................................... 19
1.9 Electroneutrality ...................................... 23
1.10 Types of Ligand ........................................ 25
2 General Properties of Organometallic Complexes .............. 33
2.1 The 18-Electron Rule ................................... 33
2.2 Limitations of the 18-Electron Rule .................... 39
2.3 Electron Counting in Reactions ......................... 41
2.4 Oxidation State ........................................ 42
2.5 Coordination Number and Geometry ....................... 46
2.6 Effects of Complexation ................................ 49
2.7 Differences between Metals ............................. 52
2.8 Supramolecular Chemistry ............................... 54
3 Metal Alkyls, Aryls, and Hydrides and Related σ-Bonded
Ligands ..................................................... 58
3.1 Transition Metal Alkyls and Aryls ...................... 58
3.2 Related σ-Bonded Ligands ............................... 73
3.3 Metal Hydride Complexes ................................ 75
3.4 σ Complexes ............................................ 78
3.5 Bond Strengths for Classical σ-Bonding Ligands ......... 82
4 Carbonyls, Phosphine Complexes, and Ligand Substitution
Reactions ................................................... 88
4.1 Metal Complexes of CO, RNC, CS, and NO ................. 88
4.2 Phosphines and Related Ligands ......................... 99
4.3 Dissociative Substitution ............................. 104
4.4 Associative Substitution .............................. 108
4.5 Redox Effects, The I Mechanism, and Rearrangements
in Substitution ....................................... 111
4.6 Photochemical Substitution ............................ 114
4.7 Steric and Solvent Effects in Substitution ............ 117
5 Complexes of Π-Bound Ligands ............................... 122
5.1 Alkene and Alkyne Complexes ........................... 122
5.2 Allyl Complexes ....................................... 128
5.3 Diene Complexes ....................................... 132
5.4 Cyclopentadienyl Complexes ............................ 136
5.5 Arenes and Other Alicyclic Ligands .................... 143
5.6 Metalacycles and Isolobal Replacement ................. 148
5.7 Stability of Polyene and Polyenyl Complexes ........... 149
6 Oxidative Addition and Reductive Elimination ............... 153
6.1 Concerted Additions ................................... 156
6.2 SN2 Reactions ......................................... 158
6.3 Radical Mechanisms .................................... 160
6.4 Ionic Mechanisms ...................................... 163
6.5 Reductive Elimination ................................. 164
6.6 σ-Bond Metathesis ..................................... 170
6.7 Oxidative Coupling and Reductive Fragmentation ........ 172
7 Insertion and Elimination .................................. 177
7.1 Reactions Involving CO ................................ 179
7.2 Insertions Involving Alkenes .......................... 185
7.3 Other Insertions ...................................... 191
7.4 α, β, γ, and δ Elimination ............................ 192
8 Nucleophilic and Electrophilic Addition and Abstraction .... 199
8.1 Nucleophilic Addition to CO ........................... 202
8.2 Nucleophilic Addition to Polyene and Polyenyl
Ligands ............................................... 204
8.3 Nucleophilic Abstraction in Hydrides, Alkyls, and
Acyls ................................................. 212
8.4 Electrophilic Addition ................................ 213
8.5 Electrophilic Abstraction of Alkyl Groups ............. 216
8.6 Single-Electron Transfer Pathways ..................... 218
8.7 Reactions of Organic Free Radicals with Metal
Complexes ............................................. 219
9 Homogeneous Catalysis ...................................... 225
9.1 Alkene Isomerization .................................. 229
9.2 Alkene Hydrogenation .................................. 231
9.3 Alkene Hydroformylation ............................... 244
9.4 Hydrocyanation of Butadiene ........................... 247
9.5 Alkene Hydrosilylation and Hydroboration .............. 250
9.6 Coupling Reactions .................................... 252
9.7 Organometallic "Oxidase" Reactions .................... 254
9.8 Surface and Supported Organometallic Catalysis ........ 255
10 Physical Methods in Organometallic Chemistry ............... 263
10.1 Isolation ............................................. 263
10.2 1H NMR Spectroscopy ................................... 264
10.3 13C NMR Spectroscopy .................................. 268
10.4 31P NMR Spectroscopy .................................. 270
10.5 Dynamic NMR ........................................... 272
10.6 Spin Saturation Transfer .............................. 276
10.7 T1 and the Nuclear Overhauser Effect .................. 277
10.8 Isotopic Perturbation of Resonance .................... 280
10.9 IR Spectroscopy ....................................... 283
10.10 Crystallography ...................................... 286
10.11 Other Methods ........................................ 288
11 Metal-Ligand Multiple Bonds ................................ 296
11.1 Carbenes .............................................. 296
11.2 Carbynes .............................................. 311
11.3 Bridging Carbenes and Carbynes ........................ 313
11.4 N-Heterocyclic Carbenes ............................... 315
11.5 Multiple Bonds to Heteroatoms ......................... 319
12 Applications of Organometallic Chemistry ................... 327
12.1 Alkene Metathesis ..................................... 327
12.2 Dimerization, Oligomerization, and Polymerization of
Alkenes ............................................... 334
12.3 Activation of CO and CO2 .............................. 343
12.4 C-H Activation ........................................ 348
12.5 Organometallic Materials and Polymers ................. 354
13 Clusters, Nanoparticles, Materials, and Surfaces ........... 361
13.1 Cluster Structures .................................... 362
13.2 Structures ............................................ 362
13.3 The Isolobal Analogy .................................. 374
13.4 Nanoparticles ......................................... 378
13.5 Giant Molecules ....................................... 381
13.6 Organometallic Materials .............................. 381
14 Applications to Organic Synthesis .......................... 388
14.1 Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond
Formation ............................................. 389
14.2 Metathesis ............................................ 396
14.3 Rhodium Carbenes in Cyclopropanation and С—Н
Insertion ............................................. 397
14.4 Hydrogenation and Related Reactions ................... 399
14.5 Carbonylation ......................................... 401
14.6 Oxidation ............................................. 405
14.7 C-H Activation ........................................ 408
14.8 Click Chemistry ....................................... 412
14.9 Noncatalytic Reactions ................................ 413
15 Paramagnetic, High-Oxidation-State, and High-
Coordination-Number Complexes .............................. 421
15.1 Magnetism and Spin States ............................. 422
15.2 Polyalkyls ............................................ 429
15.3 Polyhydrides .......................................... 434
15.4 Cyclopentadienyl Complexes ............................ 437
15.5 ƒ-Block Complexes ..................................... 439
16 Bioorganometallic Chemistry ................................ 448
16.1 Introduction .......................................... 448
16.2 Coenzyme B12 .......................................... 454
16.3 Nitrogen Fixation ..................................... 460
16.4 Nickel Enzymes ........................................ 467
16.5 Biomedical Applications ............................... 472
Useful Texts on Allied Topics ................................. 477
Major Reaction Types .......................................... 479
Solutions to Problems ......................................... 481
Index ......................................................... 496
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