Preface ........................................................ ix
List of Contributors ........................................... xi
1 New Light on the Chemistry of the Group 13 Metals ............ 1
Anthony J. Downs and Hans-Jörg 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(Il) 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 Schnöckel 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 О 'Brien
10.1 Introduction ......................................... 612
10.2 Ill-Nitrides ......................................... 619
10.3 Ill-Phosphides ....................................... 627
10.4 Ill-Arsenides ........................................ 631
10.5 III-Antimonides ...................................... 636
References ................................................. 645
11 Group 13 Metal-Mediated Organic Reactions .................. 654
Samuel Dagorne and Stéphane Bellemin-Laponnaz
11.1 Aluminium ............................................. 654
11.2 Gallium ............................................... 675
11.3 Indium ................................................ 681
11.4 Thallium .............................................. 688
References ................................................. 692
Index ......................................................... 701
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