The Group 13 Metals Aluminium, Gallium, Indium and Thallium

Dr Simon Aldridge Dr Aldridge's research interests are in main group and transition metal organometallic chemistry, low coordinate metal systems, and Lewis acids in catalysis and sensors. He is the current chairman of the RSC Main Group Chemistry interest group, and winner of RSC Dalton Transactions European Lectureship for 2009-10. Professor Anthony J. Downs The scopy of Professor Downs' research takes in the synthesis and chemistry of novel inorganic and organometallic compounds, mostly of the typical elements but also of transition metals. He has authored or edited more than 200 publications, including 27 books and review articles.

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