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ОбложкаBochmann M. Organometallics and catalysis: an introduction. - Oxford: Oxford university press, 2015. - xviii, 410 p.: tab. - Bibliogr.: p.391-404. - Ind.: p.405-410. - ISBN 978-0-19-966821-2
Шифр: (И/Г2-B69) 02
 

Место хранения: 02 | Отделение ГПНТБ СО РАН | Новосибирск

Оглавление / Contents
 
Preface ......................................................... v
General Information .......................................... viii
Ligand Nomenclature ............................................. x

1    Organometallic Compounds of Main Group Elements ............ 1
1.1  General and Bonding Considerations ......................... 2
       Box 1.1 Lithium ion intercalation ........................ 7
     Key points ................................................. 7
     Exercises .................................................. 7
1.2  Alkali Metal Organometallics: Lithium ...................... 8
     1.2.1  Synthesis ........................................... 8
     1.2.2  StructureofLithiumAlkyls ........................... 10
     1.2.3  Reactivity of Lithium Alkyls ....................... 11
     1.2.4  Organometallic Compounds of the Heavier Alkali
            Metals: Na-Cs ...................................... 15
       Box 1.2.4  Mixed-metal complexes and superbases ......... 17
     Key points ................................................ 16
     Exercises ................................................. 16
1.3  Organometallic Compounds of Alkaline Earth Metals ......... 18
     1.3.1  Beryllium .......................................... 18
     1.3.2  Magnesium .......................................... 18
       1.3.2.1  Synthesis ...................................... 18
       1.3.2.2  Structures of Magnesium Reagents ............... 23
       1.3.2.3  Reactions of Magnesium Reagents ................ 24
       Box 1.3.2  Grignard reagents ............................ 19
     1.3.3  Calcium, Strontium, and Barium ..................... 25
       Box1.3.3  Unusual Ca(1) compound ........................ 27
     Key points ................................................ 27
     Exercises ................................................. 27
1.4  Zinc, Cadmium, and Mercury ................................ 28
     1.4.1  Zinc Compounds ..................................... 28
       Box 1.4.1. Zinc alkyl purification ...................... 29
     1.4.2  Cadmium Compounds .................................. 32
     1.4.3  Mercury Compounds .................................. 33
       1.4.3.1  Synthesis ...................................... 33
       1.4.3.2  Structural Aspects ............................. 35
       Box 1.4.3 Organomercury compounds in vivo ............... 36
     Key points ................................................ 37
     Exercises ................................................. 37
1.5  Organometallic Compounds of the Boron Group ............... 38
     1.5.1  Boron Compounds .................................... 38
       1.5.1.1  Synthetic Methods .............................. 43
       1.5.1.2  Reactivityof Boron Compounds ................... 44
       1.5.1.3  Structure and Bonding .......................... 44
       Box 1.5.1.1  The importance of steric factors:
                    stabilization of a transition state ........ 42
       Box 1.5.1.2  Boron in uncommon bonding situations ....... 45
       Box 1.5.1.3  Determination of Lewis acidity ............. 45
       Box 1.5.1.4  Substituent effects in boranes: C6F5
                    versus C6H5 ................................ 46
     1.5.2  Aluminium .......................................... 46
       1.5.2.1  Synthesis ...................................... 46
       1.5.2.2  Structures and Properties ...................... 48
       Box 1.5.2.1 27Al NMR spectroscopy ....................... 49
       Box 1.5.2.2  Low-coordinate organoaluminium cations ..... 50
       1.5.2.3  Reactivity ..................................... 51
       Box 1.5.2.3  The structure and function of MAO .......... 53
       1.5.2.4  Aluminium Compounds in Low Oxidation States .... 54
     1.5.3  Gallium, Indium, and Thallium ...................... 55
       1.5.3.1  Compounds in the Oxidation State III ........... 56
       1.5.3.2  Ga, In, Tl Compounds in Low Oxidation States ... 58
       Box 1.5.3.1 Low-valent metal alkyls and aryls ........... 60
       Box 1.5.3.2 Metal alkyls as semiconductor precursors .... 62
     Key points ................................................ 63
     Exercises ................................................. 63
1.6  Organometallic Compounds of the Carbon Group .............. 64
     1.6.1  Silicon Compounds .................................. 64
       1.6.1.1  Synthetic Methods .............................. 64
       1.6.1.2  Reactivity ..................................... 65
       Box 1.6.1.2  Silicone polymers .......................... 66
       1.6.1.3  Compounds of Low-ValentSi ...................... 68
       Box 1.6.1.3  29Si NMR Spectroscopy ...................... 71
     1.6.2  Germanium .......................................... 71
     1.6.3  Tin Compounds ...................................... 71
       Box 1.6.3  Toxicity of tin(IV) reagents ................. 72
       1.6.3.1  Synthesis of Tin Compounds ..................... 72
       1.6.3.2  Structures of Sn(IV) Compounds ................. 73
       1.6.3.3  Reactivity of Tin Compounds .................... 74
       1.6.3.4  Tin in Oxidation States +111 and +11:
                Sn-Sn Bonds, Tin Radicals, and Stannylenes ..... 77
       Box 1.6.3.1  Tin(II) and lone electron pairs ............ 78
       Box 1.6.3.2  119Sn NMR spectroscopy ..................... 78
     1.6.4  Lead Compounds ..................................... 79
     Key points ................................................ 80
     Exercises ................................................. 80

2    Organometallic Compounds of Transition Metals ............. 81
       Box 2.0  Electron configuration and d-electron count .... 82
2.1  Ligand Types .............................................. 84
2.2  Common Types of Organometallic Complexes .................. 86
2.3  Electron Counting and the 16/18-Electron Rule ............. 91
     2.3.1  Counting Conventions ............................... 91
     2.3.2  Electron Counting and Oxidation States ............. 92
     Key points ................................................ 95
     Exercises ................................................. 95
2.4  Ligand Properties and Metal-Ligand Bonding ................ 96
     2.4.1  Carbon Monoxide .................................... 96
       Box 2.4.1  CO reactivity ................................ 99
     2.4.2  Alkene and Alkyne Ligands .......................... 98
       Box 2.4.2  13C NMR spectroscopy ........................ 101
     2.4.3  n-Donor Ligands ................................... 101
     2.4.4  Phosphines, Carbenes: Electronic and Steric
            Parameters ........................................ 102
     2.4.5  Common Co-Ligands ................................. 107
     Key points ............................................... 109
     Exercises ................................................ 109
2.5  L-Type n-Acceptor Ligands: Metal Carbonyl Complexes ...... 110
     2.5.1  Synthesis of Metal Carbonyls ...................... 110
       Box 2.5.1  Metal carbonyl complexes in biology
                and medicine .................................. 112
     2.5.2  Bondingin Binuclearand Cluster Complexes .......... 113
     Key points ............................................... 118
     Exercises ................................................ 118
     2.5.3  Reaction Mechanisms of Metal Carbonyls ............ 118
       2.5.3.1  Ligand Substitution: Principles and
                Mechanisms .................................... 118
       2.5.3.2  CO Ligand Substitution: Overview and Methods .. 122
       2.5.3.3  Nucleophilic Attack on CO ..................... 124
       Box 2.5.3  Nucleophilic attack on CO for hydrogen
                  production .................................. 125
     2.5.4  Metal Carbonyl Anions ............................. 125
     2.5.5  Metal Carbonyl Cations ............................ 128
     2.5.6  Metal Carbonyl Halides ............................ 129
     2.5.7  Metal Carbonyl Hydrides ........................... 130
       2.5.7.1  Syntheses ..................................... 130
       2.5.7.2  Reactions ..................................... 132
       Box 2.5.7  CO reduction: the Fischer-Tropsch process ... 134
     2.5.8  Related n-Acceptor Ligands ........................ 134
       2.5.8.1  CS, CSe, and CTe .............................. 134
       2.5.8.2  Isocyanide Complexes .......................... 135
       2.5.8.3  Nitrosyl Complexes ............................ 136
     Key points ............................................... 137
     Exercises ................................................ 137
2.6  L-Type n-Acceptor Ligands: Alkenes, Dienes, and Alkynes .. 139
     2.6.1  Alkene Complexes .................................. 141
       2.6.1.1  Synthesis of Alkene Complexes ................. 141
       2.6.1.2  Reactions of Alkene Complexes ................. 145
     2.6.2  Diene Complexes ................................... 150
       2.6.2.1  Synthesis of Conjugated Diene Complexes ....... 150
       2.6.2.2  Bonding in Complexes of Conjugated Dienes ..... 151
       Box 2.6.2.2  Molecular wires and switches .............. 154
       2.6.2.3  Reactions of Conjugated Diene Complexes ....... 153
       Box 2.6.2.3  Nucleophilic attack on n-ligands:
                    the Davies-Green-Mingos rules ............. 157
     2.6.3  Alkyne Complexes .................................. 158
       2.6.3.1  Synthesis of Alkyne Complexes ................. 160
       2.6.3.2  Reactivity of Alkyne Complexes ................ 161
       Box 2.6.3  Alkyne complexes in organic synthetic
                  methodology ................................. 165
     Key points ............................................... 168
     Exercises ................................................ 168
2.7  LX- and L2X-Typen-Ligands: Allyl and Enyl Complexes ...... 169
     2.7.1  Metal Allyl Complexes ............................. 169
       2.7.1.1  Synthesis ..................................... 169
       2.7.1.2  Properties .................................... 171
       2.7.1.3  Reactivity of Allyl Complexes ................. 172
       Box 2.7.1.3  Metal allyl catalysts ..................... 175
     2.7.2  Metal Dienyl and Trienyl Complexes ................ 177
       2.7.2.1  Synthesis ..................................... 177
       2.7.2.2  Reactivity .................................... 178
       Box 2.7.2.2  Metal dienyl complexes in organic
                    synthesis ................................. 178
     Key points ............................................... 179
     Exercises ................................................ 179
2.8  L2X-Type n-Acceptor Ligands: Metallocene Complexes ....... 180
     2.8.1  Bis(cyclopentadienyl) Complexes ................... 180
       2.8.1.1  Synthesis of Metallocene Complexes ............ 185
       2.8.1.2  Structure and Bonding in MCp2 Complexes ....... 185
       2.8.1.3  Reactions of MCp2 Complexes ................... 188
       Box 2.8.1.3  Ferrocenes in medicine and catalysis ...... 191
     2.8.2  Bent Metallocene Complexes ........................ 194
       2.8.2.1  Synthesis of Bent Sandwich Complexes .......... 194
       2.8.2.2  Structures of Bent Metallocene Complexes ...... 196
       2.8.2.3  Reactivity of Bent Metallocene Complexes ...... 198
       Box 2.8.2.1  Structural aspect of electrophilic
                    metallocenes: square-planarand trigonal-
                    bipyramidal С ............................. 201
       Box 2.8.2.2  Metallocene materials: single-molecule
                    magnets (SMMs) ............................ 203
     Key points ............................................... 204
     Exercises ................................................ 204
     2.8.3  Mono-Cyclopentadienyl (Half-Sandwich) Complexes ... 204
       2.8.3.1  Synthesis of Mono-Cp Complexes ................ 205
       2.8.3.2  Reactivity of Mono-Cp Complexes ............... 207
       Box 2.8.3  Half-sandwich complexes in stereoselective
                  synthesis ................................... 209
     Key points ............................................... 211
     Exercises ................................................ 211
2.9  Arene Complexes .......................................... 212
     2.9.1  Bis(Arene) Sandwich Complexes ..................... 212
       2.9.1.1  Synthesis and Structures ...................... 212
       2.9.1.2  Reactivity of Bis(Arene) Complexes ............ 214
     2.9.2  Arene Half-Sandwich Complexes ..................... 215
       2.9.2.1  Synthesis and Structures of Mono-Arene
                Complexes ..................................... 216
       Box2.9.2.1  Mono-arenecomplexesforcancertreatment ...... 217
       2.9.2.2  Reactivity of Mono-Arene Carbonyl Complexes ... 218
     2.9.3  Arene Complexes with Less Common Coordination
            Modes ............................................. 221
     2.9.4  Larger Arene Ligands: 7-, 8- and 9-Membered
            Rings ............................................. 222
       2.9.4.1  n-C7H7 Complexes .............................. 222
       2.9.4.2  n-C8H8 Complexes .............................. 223
       2.9.4.3  n-C9H9 Complexes .............................. 225
       2.9.4.4  n-Complexes of Heterocycles ................... 225
     Key points ............................................... 227
     Exercises ................................................ 227
2.10 Sigma Complexes .......................................... 228
     2.10.1 H2 Complexes ...................................... 228
     2.10.2 Alkane and Silane complexes ....................... 229
       Box 2.10.2 Alkane dehydrogenation and
                  functionalization ........................... 232
     Key points ............................................... 234
2.11 Complexes with M-Co-Bonds ................................ 235
     2.11.1 Energeticsand Reactivity of Metal Alkyls .......... 235
     2.11.2 Types and Bonding Modes of M-C σ-Bonded Ligands ... 237
       2.11.2.1 M-R Ligand Types .............................. 237
       2.11.2.2 M-R Bonding Modes ............................. 238
       2.11.2.3 The Importance of Steric Hindrance ............ 240
     2.11.3 Synthesis of Metal Alkyls ......................... 242
       2.11.3.1 Synthesis of Homoleptic Metal Alkyl 
                Complexes ..................................... 242
       Box 2.11.3.1 The structures of homoleptic metal methyl
                  complexes ................................... 245
       2.11.3.2 Synthesis of Heteroleptic Metal Alkyl
                Complexes ..................................... 245
       Box 2.11.3.2 Synthetic examples ........................ 252
       2.11.3.3 Alkynyl Complexes ............................. 256
     2.11.4 Reactivity of Metal Alkyls ........................ 257
       2.11.4.1 M-C Bond Protonolysis ......................... 258
       2.11.4.2 Cleavage by Halogens .......................... 259
       2.11.4.3 Chalcogen Insertions .......................... 259
       2.11.4.4 Cleavage by Lewis Acids ....................... 260
       2.11.4.5 Cleavage by Oxidation ......................... 260
       2.11.4.6 Hydrogenolysis of M-C Bonds ................... 261
       2.11.4.7 Insertion of Electrophilic Heterocumulenes .... 261
       Box 2.11.4.7 CO2 utilization in synthesis .............. 262
       2.11.4.8 Insertion of NO ............................... 263
       2.11.4.9 Insertion of CO ............................... 263
       2.11.4.10 Insertion of Isocyanides ..................... 267
       2.11.4.11 Insertion of Alkenes ......................... 268
       2.11.4.12 Insertion of Alkynes ......................... 270
       2.11.4.13 Reactions of Metal Alkyls with Non-Innocent
                 Ligands ...................................... 271
       Box 2.11.4.12 Transition metal alkyl complexes
                     in vivo .................................. 272
     Key points ............................................... 274
     Exercises ................................................ 274
2.12 Alkylidene Complexes ..................................... 275
       Box 2.12  NMR spectroscopy of metal carbenes ........... 276
     2.12.1 Synthesis of Alkylidene Complexes ................. 276
       2.12.1.1 Synthesis of Alkylidene Complexes in Low
                Oxidation States: Fischer Carbenes ............ 276
       2.12.1.2 Synthesis of Alkylidene Complexes in High
                Oxidation States (d0) ......................... 279
       2.12.1.3 Vinylidene Complexes .......................... 281
       Box 2.12.1.2 Alkynyl-allenylidene rearrangements ....... 282
     2.12.2 Reactivity of Alkylidene Complexes ................ 282
       2.12.2.1 Reactions of Fischer Carbenes ................. 282
       Box 2.12.2.1 The Dötz reaction ......................... 284
       2.12.2.2 Reactions of d0 Alkylidene Complexes .......... 283
       2.12.2.3 Ruthenium Carbene Complexes ................... 288
       Box 2.12.2.3 Applications of Olefin Metathesis ......... 289
     Key points ............................................... 292
     Exercises ................................................ 292
2.13 Complexes with M ≡ C Triple Bonds: Carbynes .............. 293
     2.13.1 Synthesis of Carbyne Complexes .................... 293
     2.13.2 Reactions of Carbyne Complexes .................... 295
     2.13.3 Bridging Carbene and Carbyne Complexes ............ 296
     Key points ............................................... 297
     Exercises ................................................ 297

3    Homogeneous Catalysis with Organometallic Transition
     Metal Complexes .......................................... 299
3.1  General Considerations ................................... 301
3.2  Key Reaction Steps in Homogeneous Catalysis .............. 304
     3.2.1  Catalyst Activation ............................... 304
     3.2.2  Oxidative Addition ................................ 305
     3.2.3  Reductive Elimination ............................. 307
     3.2.4  Nucleophilic Attack on Coordinated Substrates ..... 309
     Key points ............................................... 309
     Exercises ................................................ 310
3.3  Catalytic H-H and H-X Additions .......................... 311
     3.3.1  Hydrogenation ..................................... 311
       3.3.1.1  General hydrogenation Catalysis ............... 311
       3.3.1.2  Arene Hydrogenation ........................... 314
       3.3.1.3  Asymmetric Hydrogenation ...................... 315
       Box 3.3.1.3  Applications of asymmetric
                    hydrogenations ............................ 319
       3.3.1.4  Transfer hydrogenation ........................ 321
       Box 3.3.1.4  Hydrogen storage molecules and H2
                    release ................................... 322
       3.3.1.5  Outer-Sphere hydrogenation of Ketones ......... 322
     3.3.2  Hydrosilylation ................................... 323
     3.3.3  Isomerizations .................................... 324
     3.3.4  Hydrocyanation .................................... 325
       Box 3.3.4  Applications of asymmetric hydrocyanation ... 328
     3.3.5  Hydroamination .................................... 329
     Key points ............................................... 330
     Exercises ................................................ 331
3.4  Catalytic Carbonylations ................................. 332
     3.4.1  Hydroformylation .................................. 332
     3.4.2  Carbonylation Reactions ........................... 334
       3.4.2.1  Alcohol Carbonylations ........................ 334
       3.4.2.2  Alkene and Alkyne Carbonylations .............. 336
     Key points ............................................... 339
     Exercises ................................................ 340
3.5  Alkene Oxidations ........................................ 341
     Key points ............................................... 342
3.6  Coupling Reactions ....................................... 343
     3.6.1  C-C Cross-Coupling Reactions ...................... 344
     3.6.2  C-N Cross-Coupling Reactions ...................... 345
     3.6.3  Coupling Reactions with Carbonylation ............. 345
     3.6.4  HeckArylations .................................... 346
       Box  3.6.4  Mechanistic aspects of the Heck reaction ... 346
     Key points ............................................... 347
     Exercises ................................................ 347
3.7  Alkene Polymerizations ................................... 349
     3.7.1  Ziegler Catalysts ................................. 349
       3.7.1.1  Catalyst Composition .......................... 349
       Box 3.7.1.1  Polymersand polymer structure ............. 350
       3.7.1.2  Mechanism of Ziegler Catalysts ................ 353
     3.7.2  Metal Complexes as Polymerization Catalysts ....... 355
       3.7.2.1  Catalyst Activation and Active Species ........ 356
       3.7.2.2  Alkene Polymerization Reactions ............... 359
       3.7.2.3  Stereoselective Polymerization ................ 362
       Box 3.7.2.3  Chain-shuttling polymerization ............ 365
     3.7.3  Alkene Oligomerizations ........................... 366
       Key points ............................................. 368
       Exercises .............................................. 368
Appendix 1  Commonly Used Solvents and Their Properties ....... 369
Appendix 2  Number and Symmetry of Infrared-Active
            Vibrations of Metal Carbonyl Complexes ............ 373
Appendix 3  Answers to Exercises .............................. 374
Appendix 4  Further Reading ................................... 393
Index ......................................................... 405

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