Introduction .................................................... 1
1 Organization of the text ..................................... 1
2 Frontiers of organometallic chemistry ........................ 2
3 Situation of the book with respect to teaching ............... 2
4 Reference books and other selected references ................ 3
History of organometallic chemistry ............................. 5
1760-1900: The first complexes .................................. 5
1900-1950: Grignard, Sabatier, and catalysis in Germany ......... 6
1950-1960: The discovery of ferrocene and the boom of
organometallic chemistry ........................................ 7
1961-1981: The discovery of multiple metal-carbon bonds
and the golden age of catalysis ................................. 9
1970-1985: Activation of C-H bonds in hydrocarbons, a-bond
metathesis and H2 as a ligand .................................. 16
Current trends ................................................. 18
Part I
Structures of the transition-metal complexes
Chapter 1 - Monometallic transition-metal complexes ............ 23
1 The ligands ................................................. 23
2 The characteristics of the transition-metal in the
complexes ................................................... 32
3 Hapticity of the ligands and linear writing of the complex
formulas .................................................... 36
4 The "18-electron rule": tendencies and exceptions ........... 37
5 Bonding between the transition metal and the л-acceptor
(CO, C2H4) and π-donor ligands (halogeno, alkoxy, amino) .... 41
6 Molecular orbital diagrams .................................. 44
Summary and Exercises .......................................... 45
Chapter 2 - Bimetallic transition-metal complexes and
clusters ....................................................... 47
1 The metal-metal bond in bimetallic complexes ................ 48
Types of molecular magnetism ................................ 59
2 Clusters .................................................... 60
3 The isolobal analogy ........................................ 73
Summary and Exercises .......................................... 76
Part II
The stoichiometric reactions of transition-metal complexes
Chapter 3 - Redox reactions, oxidative addition and σ-bond
metathesis ..................................................... 81
1 Outer-sphere electron transfer .............................. 81
2 Inner-sphere electron- and atom transfer .................... 85
3 Oxidative addition, reductive elimination and σ-bond
metathesis .................................................. 87
Summary and Exercises ......................................... 106
Chapter 4 - Reactions of nucleophiles and electrophiles with
complexes ......................................... 109
1 Nucleophilic reactions ..................................... 109
2 Reactions of electrophiles ................................. 115
Summary and Exercises ......................................... 119
Chapter 5 - Ligand substitution reactions ..................... 121
1 Introduction ............................................... 121
2 "Pairwise" mechanisms ...................................... 121
3 Electron-transfer-chain and atom-transfer-chain
mechanisms ................................................. 127
4 Substitution of XLn ligands (n = 0-2) ...................... 132
Summary and Exercises ......................................... 133
Chapter 6 - Insertion and extrusion reactions ................. 135
1 Introduction ............................................... 135
2 CO 1,1 migratory insertion ................................. 136
3 Methylene insertion and extrusion .......................... 139
4 1,2 migratory insertion of alkenes and alkynes into M-H
bonds ...................................................... 140
5 Insertion of alkenes into metal-alkyl bonds and the
reverse reaction: C-C activation by β-alkyl elimination .... 142
6 α and γ-elimination ........................................ 143
Summary and Exercises ......................................... 146
Part III
The main families of organometallic complexes
Chapter 7 - Metal carbonyls and complexes of other monohapto
L ligands ..................................................... 151
1 Introduction ............................................... 151
2 Syntheses .................................................. 152
3 Binding modes .............................................. 153
4 Reactions .................................................. 159
5 Ligands isoelectronic to CO: CNR, CS, CSe, N2 and NO+ ...... 162
6 DioxygenO2 ................................................. 168
7 Phosphanes ................................................. 168
8 Weak L ligands and their role to generate organometallic
Lewis acids ................................................ 171
Summary and Exercises ......................................... 172
Cluster 8 - Metal-alkyl and -hydride complexes and other
complexes of monohapto X ligands .............................. 175
1 Different types of sp3 metal-carbon bonds .................. 175
2 Stability of metal-alkyl complexes ......................... 175
3 Synthesis of metal-alkyl complexes ......................... 179
4 Properties of metal-alkyl complexes ........................ 180
5 Metallocycles .............................................. 181
6 Metal-aryl, -vinyl, -alkynyl, -silyl, and -stannyl
complexes .................................................. 182
7 Metal-hydrides and the dihydrogen ligand ................... 184
8 Alkoxy and amido complexes ................................. 193
Summary and Exercises ......................................... 194
Chapter 9 - Metal-carbene and -carbyne complexes and
multiple bonds with transition metals ......................... 197
1 Metal-carbene complexes .................................... 197
2 Metal-carbyne complexes .................................... 215
3 Multiple bond between a heteroatom and a transition
metal: oxo, imido, phosphinidene and nitrido ligands ....... 217
Summary and Exercises ......................................... 223
Chapter 10 - π complexes of mono- and polyenes and enyls ...... 225
1 Metal-olefin complexes ..................................... 225
2 Metal-diene complexes and analogues ........................ 228
3 Metal-alkyne complexes ..................................... 231
4 π-Allyl complexes ......................................... 233
5 Polyenyl complexes ......................................... 237
6 Arene complexes ............................................ 242
Summary and Exercises ......................................... 248
Chapter 11 - Metallocenes and sandwich complexes .............. 251
1 Structure of the metallocenes .............................. 251
2 Redox properties of the sandwich metallocenes .............. 255
3 Metallocene synthesis ...................................... 256
4 Chemical properties of metallocenes ........................ 258
5 Triple- and multiple-decker sandwich complexes ............. 266
6 Non-sandwich metallocenes derivatives ...................... 268
7 Metal-bis-arene sandwich complexes ......................... 270
8 Cylopentadienyl-metal-arene complexes ...................... 274
Summary and Exercises ......................................... 287
Chapter 12 - Ionic and polar metal-carbon bonds: alkali and
rare-earth complexes .......................................... 289
1 Introduction ............................................... 289
2 Organometallic complexes of alkali metals .................. 289
3 Grignard reagents .......................................... 293
4 The scandium, ytrium, lanthanides and actinides complexes .. 296
Summary and Exercises ......................................... 310
Chapter 13 - Covalent chemistry of the organoelements
of frontier (11,12) and main (13-16) groups ................... 313
1 Introduction ............................................... 313
2 Group 11 (Cu, Ag, Au) ...................................... 314
3 Group 12 (Zn, Cd, Hg) ...................................... 316
4 Group 13 (В, AI, Ga, In, Tl) ............................... 320
5 Group 14 (Si, Ge, Sn, Pb) .................................. 328
6 Group 15 (As, Sb, Bi) ...................................... 340
7 Group 16 (Se, Те) .......................................... 344
Summary and Exercises ......................................... 346
Part IV Catalysis
Introduction to catalysis ..................................... 351
Chapter 14 - Hydrogenation and hydroelementation of alkenes ... 357
1 Hydrogenation of olefins ................................... 357
2 Asymmetric hydrogenation ................................... 360
4 Hydroboration of olefins ................................... 362
5 Hydrocyanation of olefins .................................. 362
6 Hydroamination of olefins and alkynes ...................... 363
Summary and Exercises ......................................... 364
Chapter 15 - Transformations of alkenes and alkynes ........... 367
1 Ziegler-Natta-type olefin polymerization ................... 367
2 Metathesis of alkenes, alkynes and cycloalkenes ............ 373
3 Olefin dimerization and oligomerization .................... 386
4 Olefin isomerization ....................................... 390
Summary and Exercises ......................................... 392
Chapter 16 - Oxidation of olefins ............................. 395
1 Historic introduction and radical-type oxidation ........... 395
2 Ethylene oxidation to acetaldehyde: Wacker process ......... 396
4 Epoxidation of olefins ..................................... 399
5 Hydroxylation by metal-oxo complexes ....................... 402
6 Phase-transfer catalysis in oxidation chemistry ............ 405
Summary and Exercises ......................................... 407
Chapter 17 - C-H activation and functionalization of
alkanes and arenes ............................................ 409
1 Introduction ............................................... 409
2 Alkanes and cycloalkanes ................................... 410
3 Aromatics .................................................. 419
Summary and Exercises ......................................... 428
Chapter 18 - Carbonylation and carboxylation reactions ........ 431
1 Carbonylation of methanol: Monsanto process ................ 431
2 Olefin hydroformylation: oxo process ....................... 433
3 Carbonylation of alkenes and alkynes in the presence of
a nucleophile: the Reppe reaction .......................... 434
4 Carbonylation of aryl halides in the presence of a
nucleophile ................................................ 436
5 Catalysis of СO2 transformation ............................ 437
Summary and Exercises ......................................... 438
Chapter 19 - Bio-organometallic chemistry: enzymatic
catalysis ..................................................... 441
1 Introduction ............................................... 441
2 Cobalamin: co-enzyme vitamin B12 ........................... 442
3 Biological redox mediators ................................. 445
4 Examples of oxido-reductase enzymes: the mono-oxygenases ... 446
5 Nitrogen fixation by nitrogenase enzyme .................... 448
6 Nickel enzymes ............................................. 452
Summary and Exercises ......................................... 455
Chapter 20 Heterogeneous catalysis ............................ 457
1 Introduction ............................................... 457
2 Concepts of heterogeneous catalysis ........................ 460
3 CO and CO2 hydrogenation and Fischer-Tropsch chemistry ..... 469
4 Transformation of hydrocarbons ............................. 475
5 Metathesis of alkanes, alkenes and alkynes ................. 477
6 Oxidation of hydrocarbons .................................. 480
7 Nanoparticle catalysis: the fast growing frontier between
homogeneous and heterogeneous catalysis .................... 483
Summary and Exercises ......................................... 485
Part V
Applications in organic synthesis
Chapter 21 - Organometallic complexes in organic synthesis
Examples of applications ...................................... 489
1 Protection and stabilization of unsaturated organic
derivatives and fragments .................................. 489
2 Nucleophilic and electrophilic reactions on hydrocarbon
ligands .................................................... 492
3 General methods of C-C bond formation using the oxidative
addition of an organic halide or a related electrophile .... 497
4 Extension of palladium catalysis to the formation of C-O
and C-N bonds .............................................. 516
5 Oxidative coupling reactions of alkynes with other
unsaturated fragments for the formation of cyclic and
heterocyclic compounds ..................................... 518
6 Metal-carbene complexes in organic synthesis ............... 521
7 Examples of asymmetric catalysis ........................... 523
Summary and Exercises ...................................... 530
Answers to exercises .......................................... 535
References .................................................... 553
Abbreviations ................................................. 591
Index ......................................................... 595
Atomic weights of the elements ................................ 609
Periodic table of the elements ................................ 611
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