Wiley.com
Print this page Share
E-book

Molecular Metal-Metal Bonds: Compounds, Synthesis, Properties

ISBN: 978-3-527-67337-7
592 pages
March 2015
Molecular Metal-Metal Bonds: Compounds, Synthesis, Properties (3527673377) cover image

Description

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.
See More

Table of Contents

Preface XV

List of Contributors XVII

1 Introduction and General Survey of Metal–Metal Bonds 1
John E. McGrady

1.1 Introduction 1

1.2 Metal–Metal Bonds Involving s Orbitals 3

1.3 Metal–Metal Bonds Involving d Orbitals 5

1.4 Metal–Metal Bonds Between f Orbitals 16

1.5 Metal–Metal Bonds Between p Orbitals 17

1.6 Concluding Remarks 19

References 20

2 s-Block Metal–Metal Bonds 23
Cameron 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 Metal–Metal Bonding Interactions, and Related Species 25

2.2.3 Stable Metal–Metal 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 2–Transition Metal Complexes 34

2.4.2 Group 2–Main Group Metal Complexes 39

References 42

3 Group 3, Lanthanide, and Actinide Metal–Metal Bonds 47
Benjamin 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 Metal–Metal 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 C–H Activation 61

3.3.3 Oxidation of the Metal–Metal Bond 62

3.4 Solid-State Structures 63

3.4.1 Typical Structures 63

3.4.2 Metal–Metal 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 Metal–Metal Bonds 73
Lutz H. Gade

4.1 Introduction 73

4.2 Homodinuclear Group 4 Complexes: Metal–Metal Bonding or Not? 73

4.3 Heterobimetallic Complexes Containing Metal–Metal Bonds Involving Group 4 Metals 74

4.3.1 Metal–Metal Bond Polarity in Early-Late Heterobimetallic Complexes Involving Group 4 Metals 75

4.3.2 Synthetic Strategies for the Generation of Highly Polar Metal–Metal Bonds 77

4.3.3 Factors Influencing the Stability of “Unsupported” Metal–Metal Bonds in Ti/Zr/Hf–M Heterodimetallic Complexes 79

4.4 Basic Patterns of Reactivity Observed for Metal–Metal Bonded Early-Late Heterodinuclear Complexes 81

4.4.1 Insertions into Polar Metal–Metal Bonds and Subsequent Transformations 82

4.4.2 Reactivity of Phosphinoamide-Bridged Zr–Co Heterobimetallic Complexes 85

4.5 Early-Late Heterobimetallic Complexes of Group 4 Metals as Potential Catalysts 85

References 88

5 Group 5 Metal–Metal Bonds 91
Sundargopal 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 126

5.4.7 μ-Acyl Complexes 127

5.4.8 Oxametallaboranes 129

5.4.9 Triply Bridged Borylene Complexes 129

References 131

6 Group 6 Metal–Metal Bonds 139
Malcolm H. Chisholm and Nathan J. Patmore

6.1 Metal–Metal 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 Metal–Metal Bonds 175
Frederic 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 175

7.1.3 Complexes with Mn23+ Core 176

7.1.4 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 186

7.2.3 Complexes with a Tc25+ Core 193

7.2.4 Complexes with a Tc24+ Core 196

7.2.5 Miscellaneous Complexes with Tc–Tc Multiple Bonds 200

7.3 Rhenium 202

7.3.1 Introduction 202

7.3.2 Complexes with the Re28+ Core 203

7.3.3 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 216

7.3.7 Complexes with the Re9+3 Core 220

References 222

8 Group 8 Metal–Metal Bonds 225
Stephen 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 Metal–Metal Bonds 279
Helen 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 Co–Co 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 Metal–Metal Bonds 325
Erli 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 Metal–Metal Bonds 397
Thomas G. Gray and Joseph P. Sadighi

11.1 Introduction 397

11.2 Formally Noncovalent Metal–Metal 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 Metal–Metal 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 Silver–Silver Bonding 418

11.3.4 Gold–Gold Bonding 419

11.4 Heterobimetallic Complexes of the Group 11 Metals 421

References 424

12 Group 12 Metal–Metal Bonds 429
Xian 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 Metal–Metal Bonds 455
Joseph 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 13–Group 13 Metal–Metal 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 467

13.4.5 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 Metal–Metal Bonds 485
Robert J. Less and Dominic S.Wright

14.1 Introduction 485

14.2 Homoatomic Group 14–Group 14 Bonds 485

14.2.1 Cluster Compounds 485

14.2.2 Group 14–Group 14 Single Bonds (E–E) 491

14.2.3 Group 14–Group 14 Double Bonds (E=E) 494

14.2.4 Group 14–Group 14 Triple Bonds (E≡E) 497

14.3 Heteroatomic Metal–Metal Bonds 499

14.3.1 s-Block Metal–Group 14 Metal Bonds 499

14.3.2 p-Block Metal–Group 14 Bonds [Group 13 (Al–Tl and Group 15 (As–Bi)] 502

14.3.3 f-Block Metal–Group 14 Bonds (including Sc, Y, La) 504

14.3.4 Transition Metal–Group 14 Bonds 505

References 511

15 Group 15 Metal–Metal Bonds 519
James S. Jones, Baofei Pan, and François P. Gabbaï

15.1 Introduction 519

15.2 Complexes with Sb–Sb and Bi–Bi 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 525

15.2.4 Compounds with Pn–Pn (Pn = Sb, Bi) Multiple Bonds 529

15.3 Complexes with M–Sb and M–Bi Bonds (M=d-Block Metal) 533

15.3.1 Complexes Containing R2Pn Fragments as Ligands (Pn=Sb or Bi) 534

15.3.2 Complexes Containing RPn Fragments as Ligands (Pn=Sb or Bi) 543

15.3.3 Complexes Containing Bridging or Terminal Pn Atoms as Ligands (Pn=Sb or Bi) 548

15.4 Metal–Antimony Bonds Involving High-Valent Antimony Fragments 549

15.5 Concluding Remarks 552

References 553

Index 559

See More

Author Information

Stephen Liddle obtained his BSc Hons (1997) and PhD (2000) from Newcastle University. After postdoctoral fellowships at Edinburgh, Newcastle, and Nottingham Universities he took up a Royal Society University Research Fellowship at Nottingham (2007) and was promoted to Associate Professor and Reader (2010). He has been awarded an ERC Starting Investigators Grant (2009, uranium-metal bonds), the RSC Sir Edward Frankland Fellowship and Bill Newton awards (2011), and he was a co-recipient of the IChemE Petronas prize for education and training (2008). He was elected as a Fellow of the Royal Society of Chemistry in 2011. He is Chairman of COST Action CM1006 and was recently elected as a Vice President of the executive committee of the European Rare Earth and Actinide Society. He is a member of the Board of Editors for Philosophical Transactions A of the Royal Society and has published over 100 primary-research and review articles to date.
See More

Related Titles

Back to Top