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The Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities



The Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities

Simon Aldridge, Anthony J. Downs

ISBN: 978-0-470-97668-5 February 2011 336 Pages

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The last two decades have seen a renaissance in interest in the chemistry of the main group elements. In particular research on the metals of group 13 (aluminium, gallium, indium and thallium) has led to the synthesis and isolation of some very novel and unusual molecules, with implications for organometallic synthesis, new materials development, and with biological, medical and, environmental relevance.

The Group 13 Metals Aluminium, Gallium, Indium and Thallium aims to cover new facts, developments and applications in the context of more general patterns of physical and chemical behaviour. Particular attention is paid to the main growth areas, including the chemistry of lower formal oxidation states, cluster chemistry, the investigation of solid oxides and hydroxides, advances in the formation of III-V and related compounds, the biological significance of Group 13 metal complexes, and the growing importance of the metals and their compounds in the mediation of organic reactions. Chapters cover:

  • general features of the group 13 elements
  • group 13 metals in the +3 oxidation state: simple inorganic compounds
  • formal oxidation state +3:  organometallic chemistry
  • formal oxidation state +2: metal-metal bonded vs. mononuclear derivatives
  • group 13 metals  in the +1 oxidation state
  • mixed or intermediate valence group 13 metal compounds
  • aluminium and gallium clusters: metalloid clusters and their relation to the bulk phases, to naked clusters, and to nanoscaled materials
  • simple and mixed metal oxides and hydroxides:  solids with extended structures of different dimensionalities and porosities
  • coordination and solution chemistry of the metals: biological, medical and, environmental relevance
  • III-V and related semiconductor materials
  • group 13 metal-mediated organic reactions

The Group 13 Metals Aluminium, Gallium, Indium and Thallium provides a detailed, wide-ranging, and up-to-date review of the chemistry of this important group of metals. It will find a place on the bookshelves of practitioners, researchers and students working in inorganic, organometallic, and materials chemistry.

Preface ix

List of Contributors xi

1 New Light on the Chemistry of the Group 13 Metals 1
Anthony J. Downs and Hans-Jo¨rg Himmel

1.1 Reprise of the General Features of Group 13 Elements 1

1.2 Developments in Methodology 6

1.3 Redox Chemistry of the Group 13 Metals: Access to Oxidation States Lower than +3 25

1.4 Bonding Aspects 28

1.5 Solid Compounds with Specific Electronic, Structural or Other Properties 38

1.6 Coordination Chemistry of M(III) Compounds 43

1.7 Mediation of Organic Transformations by Group 13 Metal Compounds 57

References 60

2 The Chemistry of the Group 13 Metals in the +3 Oxidation State: Simple Inorganic Compounds 75
Simon Aldridge

2.1 Introduction 75

2.2 Hydrides 76

2.3 Halides and Pseudo-Halides 99

2.4 Oxides and Oxo- Derivatives 107

2.5 Chalcogenides and Chalco-Derivatives 118

2.6 Compounds with Bonds to Group 15 Atoms 122

References 132

3 Formal Oxidation State +3: Organometallic Chemistry 148
Simon Aldridge, Anthony J. Downs and Deborah L. Kays

3.1 Introduction 148

3.2 Organo Derivatives with a Metal–Carbon Primary Framework 151

3.3 Derivatives with Bonds to Group 15 Elements 168

3.4 Derivatives with Bonds to Group 16 Elements 192

3.5 Organometal Halides 210

3.6 Organometal Hydrides 215

3.7 d-Block and f-Block Compounds with Organo-Group 13 Metal(III) Fragments 220

References 227

4 Formal Oxidation State +2: Metal–Metal Bonded Versus Mononuclear Derivatives 246
Werner Uhl and Marcus Layh

4.1 Introduction 246

4.2 Subhalides Containing M–M Bonds 247

4.3 Homoleptic Chalcogen Compounds 250

4.4 Homoleptic Dielement Compounds with Pnicogen Atoms Coordinated to the M–M Bonds 251

4.5 Heteroleptic Compounds Containing Donor Atoms of Groups 15 to 17 254

4.6 Homoleptic Dinuclear Organoelement(II) Compounds 257

4.7 Heteroleptic Organoelement(II) Compounds 265

4.8 Mononuclear Element(II) Compounds 274

References 277

5 The Chemistry of the Group 13 Metals in the +1 Oxidation State 285
Cameron Jones and Andreas Stasch

5.1 Introduction 285

5.2 Aluminium 286

5.3 Gallium 298

5.4 Indium 310

5.5 Thallium 317

References 329

6 Mixed or Intermediate Valence Group 13 Metal Compounds 342
Benjamin F. T. Cooper and Charles L. B. Macdonald

6.1 Mixed Valency 342

6.2 Halides 346

6.3 Arene-stabilised Mixed Valent Species 353

6.4 Chalcogenide and Other Non-Halide Salts 363

6.5 Discretely Bonded Systems 368

6.6 Donor–Acceptor Compounds 390

6.7 Conclusions 396

References 397

7 Aluminium and Gallium Clusters: Metalloid Clusters and their Relationship to the Bulk Phases, to Naked Clusters and to Nanoscaled Materials 402
Hansgeorg Schno¨ckel and Andreas Schnepf

7.1 Introduction 402

7.2 Explanations of Special Terms 404

7.3 The Naked Al13 Cluster 407

7.4 Metalloid Al/Ga Clusters 416

7.5 Interactions between Cluster Species within the Crystal 471

7.6 Summary and Outlook 480

References 482

8 Simple and Mixed Metal Oxides and Hydroxides: Solids with Extended Structures of Different Dimensionalities and Porosities 488
Andrew M. Fogg

8.1 Introduction 488

8.2 The Parent Oxides and Hydroxides 489

8.3 Layered Materials 494

8.4 Framework Materials 502

References 509

9 Coordination and Solution Chemistry of the Metals: Biological, Medical and Environmental Relevance 519
Penelope J. Brothers and Christy E. Ruggiero

9.1 Introduction 519

9.2 Hydrides 521

9.3 Halides 542

9.4 Group 13 Complexes of N-donor Ligands 548

9.5 Complexes of the Monovalent M(I) Group 13 Metals 557

9.6 Divalent M(II) Complexes 568

9.7 Chemistry Relevant to Environmental and Biological Systems 569

9.8 Environmental Abundances, Uses and Sources 572

9.9 Biological Systems 576

References 593

10 III–V and Related Semiconductor Materials 612
Mohammad Azad Malik and Paul O’Brien

10.1 Introduction 612

10.2 III–Nitrides 619

10.3 III–Phosphides 627

10.4 III–Arsenides 631

10.5 III–Antimonides 636

References 645

11 Group 13 Metal-Mediated Organic Reactions 654
Samuel Dagorne and Ste´phane Bellemin-Laponnaz

11.1 Aluminium 654

11.2 Gallium 675

11.3 Indium 681

11.4 Thallium 688

References 692

Index 701

"All the chapters in this book are written by leading experts in the corresponding research areas and offer an excellent overview of recent research. The nearly exhaustive collection of literature references reflects the state of the art up to 2009, or even 2010. The opus is a real mine of information for everyone interested in modern chemistry, for researchers, and for advanced students. Even those who have been active in triel chemistry for years will find this to be a very valuable reference work." (Angewandte Reviews, 2011)

"For this reason, I would recommend this book wholeheartedly to any inorganic or organometallic chemist with a fundamental interest in this fascinating and varied series of elements." (Applied Organometallic Chemistry, 2011)