Systematically covering all the latest developments in the field, this is a comprehensive and handy introduction to metal-metal bonding. The chapters follow a uniform, coherent structure for a clear overview, allowing readers easy access to the information. The text covers such topics as synthesis, properties, structures, notable features, reactivity and examples of applications of the most important compounds in each group with metal-metal bonding throughout the periodic table. With its general remarks at the beginning of each chapter, this is a must-have reference for all molecular inorganic chemists, including PhD students and postdocs, as well as more experienced researchers.
Preface XV
List of Contributors XVII
1 Introduction and General Survey of MetalMetal Bonds 1John E. McGrady
1.1 Introduction 1
1.2 MetalMetal Bonds Involving s Orbitals 3
1.3 MetalMetal Bonds Involving d Orbitals 5
1.4 MetalMetal Bonds Between f Orbitals 16
1.5 MetalMetal Bonds Between p Orbitals 17
1.6 Concluding Remarks 19
References 20
2 s-Block MetalMetal Bonds 23Cameron Jones, Philip Mountford, Andreas Stasch, and Matthew P. Blake
2.1 Introduction 23
2.2 Group 1 Bimetallics 23
2.2.1 Group 1 Diatomics and Related Species 23
2.2.2 Stable Complexes with Group 1 MetalMetal Bonding Interactions, and Related Species 25
2.2.3 Stable MetalMetal Bonded Complexes Involving One Group 1 Metal 25
2.3 Group 2 Homobimetallics 27
2.3.1 Group 2 Diatomics and Related Species 27
2.3.2 Transient Group 2 Metal(I)Metal(I) Bonded Dimers 28
2.3.3 Isolable Group 2 Metal(I)Metal(I) Bonded Dimers 29
2.4 Group 2 Heterobimetallics 34
2.4.1 Group 2Transition Metal Complexes 34
2.4.2 Group 2Main Group Metal Complexes 39
References 42
3 Group 3, Lanthanide, and Actinide MetalMetal Bonds 47Benjamin Oelkers and Rhett Kempe
3.1 Introduction 47
3.1.1 The Isocarbonyl Problem 48
3.2 Preparation 48
3.2.1 Salt Elimination 48
3.2.2 Alkane and Amine Elimination 51
3.2.3 Reductive Cleavage of MetalMetal Bonds 54
3.2.4 Adduct Formation 57
3.3 Reactivity 59
3.3.1 Deprotonation of Acidic Substrates 60
3.3.2 Intramolecular Deprotonation and CH Activation 61
3.3.3 Oxidation of the MetalMetal Bond 62
3.4 Solid-State Structures 63
3.4.1 Typical Structures 63
3.4.2 MetalMetal Bond Lengths 64
3.5 Theoretical Calculations and Bonding 66
3.5.1 Complexes with Rare Earth Metals 66
3.5.2 Complexes with Actinide Metals 69
References 69
4 Group 4 MetalMetal Bonds 73Lutz H. Gade
4.1 Introduction 73
4.2 Homodinuclear Group 4 Complexes: MetalMetal Bonding or Not? 73
4.3 Heterobimetallic Complexes Containing MetalMetal Bonds Involving Group 4 Metals 74
4.3.1 MetalMetal Bond Polarity in Early-Late Heterobimetallic Complexes Involving Group 4 Metals 75
4.3.2 Synthetic Strategies for the Generation of Highly Polar MetalMetal Bonds 77
4.3.3 Factors Influencing the Stability of Unsupported MetalMetal Bonds in Ti/Zr/HfM Heterodimetallic Complexes 79
4.4 Basic Patterns of Reactivity Observed for MetalMetal Bonded Early-Late Heterodinuclear Complexes 81
4.4.1 Insertions into Polar MetalMetal Bonds and Subsequent Transformations 82
4.4.2 Reactivity of Phosphinoamide-Bridged ZrCo Heterobimetallic Complexes 85
4.5 Early-Late Heterobimetallic Complexes of Group 4 Metals as Potential Catalysts 85
References 88
5 Group 5 MetalMetal Bonds 91Sundargopal Ghosh and Dipak Kumar Roy
5.1 General Remarks 91
5.2 Vanadium Complexes 91
5.2.1 Carbonyl Complexes 92
5.2.2 Amido, Imido and Nitride Complexes 92
5.2.3 Hydride, Alkyl and Aryl Complexes 95
5.2.4 Chalcogenide Complexes 97
5.2.5 Vanadaboranes 99
5.2.6 Vanadaheteroboranes 101
5.2.7 Triple-Decker Complexes 103
5.2.8 Paddlewheel Complexes 104
5.3 Niobium Complexes 106
5.3.1 Hydride, Alkyl, and Aryl Complexes 106
5.3.2 Nitride Complexes 108
5.3.3 Triple-Decker Complexes 109
5.3.4 Paddlewheel Complexes 110
5.3.5 Niobaborane and Niobaheteroboranes 111
5.4 Tantalum Complexes 114
5.4.1 Carbonyl Complexes 114
5.4.2 Hydride, Alkyl, and Aryl Complexes 114
5.4.3 Akylidene and Alkylidyne Complexes 119
5.4.4 Nitride and Phosphine Complexes 120
5.4.5 Tantalaboranes 121
5.4.6 Cluster Growth Reaction of Ditantalaboranes 1265.4.7 -Acyl Complexes 127
5.4.8 Oxametallaboranes 129
5.4.9 Triply Bridged Borylene Complexes 129
References 131
6 Group 6 MetalMetal Bonds 139Malcolm H. Chisholm and Nathan J. Patmore
6.1 MetalMetal Quadruple Bonds 139
6.1.1 Synthesis and Characterization 139
6.1.2 Molecular Assemblies 143
6.1.3 Electronic Coupling 145
6.1.4 Photophysical Studies 151
6.2 Quintuple Bonds 162
6.2.1 Discovery 162
6.2.2 Synthesis 163
6.2.3 Structure 166
6.2.4 Theoretical Studies 169
6.2.5 Reactivity 170
References 172
7 Group 7 MetalMetal Bonds 175Frederic Poineau, Alfred P. Sattelberger, Erli Lu, and Stephen T. Liddle
7.1 Manganese 175
7.1.1 Introduction 175
7.1.2 Complexes with Mn24+ Core 1757.1.3 Complexes with Mn23+ Core 1767.1.4 Complexes with Mn22+ Core 177
7.1.5 Complexes with Mn20 Core 183
7.2 Technetium 185
7.2.1 Introduction 185
7.2.2 Complexes with a Tc26+ Core 1867.2.3 Complexes with a Tc25+ Core 1937.2.4 Complexes with a Tc24+ Core 196
7.2.5 Miscellaneous Complexes with TcTc Multiple Bonds 200
7.3 Rhenium 202
7.3.1 Introduction 202
7.3.2 Complexes with the Re28+ Core 2037.3.3 Complexes with the Re27+ Core 204
7.3.4 Complexes with the Re26+ Core 205
7.3.5 Complexes with the Re25+ Core 216
7.3.6 Complexes with the Re24+ Core 2167.3.7 Complexes with the Re9+3 Core 220
References 222
8 Group 8 MetalMetal Bonds 225Stephen J. Tereniak and Connie C. Lu
8.1 Introduction 225
8.2 Group 8 Homobimetallics 225
8.2.1 Diiron 225
8.2.2 Diruthenium 237
8.2.3 Diosmium 250
8.3 Group 8 Heterometallics 256
8.3.1 Intratriad Heterometallics 257
8.3.2 Intertriad Heterometallics 258
References 272
9 Group 9 MetalMetal Bonds 279Helen T. Chifotides, Biswajit Saha, Nathan J. Patmore, Kim R. Dunbar, and Jitendra K. Bera
9.1 Cobalt 279
9.1.1 Overview 279
9.1.2 Dicobalt Compounds with Short CoCo Bonds 279
9.1.3 Cobalt Extended Metal Chains 282
9.2 Rhodium 285
9.2.1 Introduction 285
9.2.2 Catalysis 286
9.2.3 Dirhodium Complexes with Photochemical and Other Applications 303
9.2.4 Perspective 314
9.3 Iridium 315
9.3.1 Synthesis and Characterization of Diiridium Compounds 315
9.3.2 Small Molecule and Bond Activation by Diiridium Compounds 316
References 317
10 Group 10 MetalMetal Bonds 325Erli Lu and Stephen T. Liddle
10.1 Introduction 325
10.2 Bimetallic Compounds 325
10.2.1 Dinickel Compounds 326
10.2.2 Dipalladium Compounds 347
10.2.3 Diplatinum Compounds 370
10.2.4 Heterobimetallic Compounds 384
10.3 Multimetallic Sandwich Compounds a Brief Introduction 387
References 390
11 Group 11 MetalMetal Bonds 397Thomas G. Gray and Joseph P. Sadighi
11.1 Introduction 397
11.2 Formally Noncovalent MetalMetal Interactions 397
11.2.1 Copper(I)Copper(I) Interactions 398
11.2.2 Silver(I)Silver(I) Interactions 403
11.2.3 Supported and Semi-Supported Gold(I)Gold(I) Interactions 406
11.2.4 Unsupported Gold(I)Gold(I) Interactions 412
11.2.5 Metallophilic Interactions Involving Gold(III) 414
11.3 Covalent MetalMetal Bonding 415
11.3.1 Paddlewheel Complexes of Copper(II) 415
11.3.2 Mixed-Valent Copper(I)/Copper(II) Complexes 415
11.3.3 SilverSilver Bonding 418
11.3.4 GoldGold Bonding 419
11.4 Heterobimetallic Complexes of the Group 11 Metals 421
References 424
12 Group 12 MetalMetal Bonds 429Xian Wu and Sjoerd Harder
12.1 Introduction 429
12.2 Homobimetallics 430
12.2.1 Synthesis and Structures 430
12.2.2 Reactivity 434
12.3 Heterobimetallics 437
12.3.1 Bonding between G12 and Late Main Group Metals 437
12.3.2 Bonding Between G12 and Transition Metals 441
12.4 Summary and Perspectives 449
References 450
13 Group 13 MetalMetal Bonds 455Joseph A.B. Abdalla and Simon Aldridge
13.1 Preamble 455
13.2 s-Block to Group 13 Metal Bonds 455
13.2.1 Group 1 Metal Complexes 456
13.2.2 Group 2 Metal Complexes 457
13.3 p-Block to Group 13 Metal Bonds 458
13.3.1 Group 12 Metal Complexes 458
13.3.2 Group 13Group 13 MetalMetal Bonds 459
13.3.3 Group 14 Metal Complexes 464
13.4 d-Block-Group 13 Metal Bonds 464
13.4.1 Synthesis via Salt Elimination 465
13.4.2 Synthesis via Alkane Elimination 466
13.4.3 Oxidative Addition versus Adduct Formation: a Fine Electronic Balance 466
13.4.4 Metal-Only Lewis Pairs 46713.4.5 Double Salt Elimination as Access to the +1 Oxidation State 468
13.4.6 Halide Abstraction as a Route to Cationic Diyl Systems 469
13.4.7 Direct Reactions with MI Species 471
13.5 f-Block-Group 13 Metal Bonds 476
Abbreviations 477
References 477
14 Group 14 MetalMetal Bonds 485Robert J. Less and Dominic S.Wright
14.1 Introduction 485
14.2 Homoatomic Group 14Group 14 Bonds 485
14.2.1 Cluster Compounds 485
14.2.2 Group 14Group 14 Single Bonds (EE) 491
14.2.3 Group 14Group 14 Double Bonds (E=E) 494
14.2.4 Group 14Group 14 Triple Bonds (EE) 497
14.3 Heteroatomic MetalMetal Bonds 499
14.3.1 s-Block MetalGroup 14 Metal Bonds 499
14.3.2 p-Block MetalGroup 14 Bonds [Group 13 (AlTl and Group 15 (AsBi)] 502
14.3.3 f-Block MetalGroup 14 Bonds (including Sc, Y, La) 504
14.3.4 Transition MetalGroup 14 Bonds 505
References 511
15 Group 15 MetalMetal Bonds 519James S. Jones, Baofei Pan, and François P. Gabbaï
15.1 Introduction 519
15.2 Complexes with SbSb and BiBi Bonds 519
15.2.1 Synthesis and Structures of Distibines and Dibismuthines 519
15.2.2 Synthesis and Structures of cyclo-Organostibines and -Organobismuthines 523
15.2.3 Stability and Reactivity 52515.2.4 Compounds with PnPn (Pn = Sb, Bi) Multiple Bonds 52915.3 Complexes with MSb and MBi Bonds (M=d-Block Metal) 53315.3.1 Complexes Containing R2Pn Fragments as Ligands (Pn=Sb or Bi) 53415.3.2 Complexes Containing RPn Fragments as Ligands (Pn=Sb or Bi) 54315.3.3 Complexes Containing Bridging or Terminal Pn Atoms as Ligands (Pn=Sb or Bi) 548
15.4 MetalAntimony Bonds Involving High-Valent Antimony Fragments 549
15.5 Concluding Remarks 552
References 553
Index 559
