Inorganic Chemistry in Focus II

Gerd Meyer studied chemistry at the Justus-Liebig University in Giessen under the supervision of Rudolf Hoppe. He gained his doctorate in 1976, and in 1980 worked with John D. Corbett at Iowa State University. In 1982 he gained his lecturing qualification in inorganic chemistry at Giessen, becoming a Full Professor at the University of Hanover in 1988. He subsequently moved to the same position at the University of Cologne in 1996. Professor Meyer's main research interests focus on solid-state and coordination chemistry of rare-earth elements and transition elements. Dieter Naumann studied chemistry at the Rheinisch-Westfaelische Technische Hochschule (RWTH) at Aachen. His diploma (1967) and doctoral theses (1969) were supervised by Martin Schmeisser. Research on perfluoroalkyl iodine compounds led to his lecturing qualification in inorganic chemistry at the University of Dortmund in 1975. From 1967 until 1989 he was a professor in Dortmund, becoming a Full Professor of Inorganic and Analytical Chemistry at the University of Cologne in 1989. His main research interests are syntheses of fluoroorgano groups 10 to 18 element compounds. Lars Wesemann studied chemistry at the Rheinisch-Westfaelische Technische Hochschule in Aachen. His diploma and doctoral theses were supervised by Gerhard E. Herberich, and he gained the latter in 1990. After that he worked in Dietmar Seyferth's group at MIT for one year before returning to the RWTH Aachen. Independent research led him to his lecturing qualification in inorganic chemistry in 1997. He was a Professor of Inorganic Chemistry at the University of Cologne from 1999 until 2003, and is now a Full Professor at the University of Tubingen.

Preface xiii List of Contributors xv 1 On the Track of Reaction Mechanisms: Characterization and Reactivity of Metal Atom Dimers 1 Hans-Jrg Himmel 1.1 Introduction 1 1.2 Principle and Realization of the Matrix-Isolation Experiment 2 1.3 Characterization of Metal Atom Dimers 3 1.4 Reactivity of Metal Atom Dimers and Comparison with the Reactivity of Single Metal Atoms 7 1.4.1 The Reaction Between Ga2 and H2 7 1.4.2 The Reaction Between Ti2 and N2 10 1.5 Concluding Remarks 12 References 12 2 Noble Gas Hydride Compounds 15 Mika Pettersson, Leonid Khriachtchev, Jan Lundell, and Markku Rsnen 2.1 Introduction 15 2.2 Nature of Bonding 16 2.3 Computational Properties of HNgY 17 2.3.1 Molecular Structure 17 2.3.2 Stability 21 2.4 Preparative Methods 21 2.5 Spectroscopic Properties 23 2.5.1 Experimental Spectroscopic Observations 23 2.5.2 Computational Vibrational Spectra of HNgY 24 2.6 Selected Examples of HNgY Compounds 25 2.6.1 Xenon Compounds 25 2.6.2 Compounds of Lighter Noble Gases 26 2.7 HNgY Complexes 27 2.8 Reactions of HNgY Molecules with Hydrogen Atoms 29 2.9 Future Directions 31 References 32 3 Polycationic Clusters of the Heavier Group 15 and 16 Elements 35 Johannes Beck 3.1 Introduction 35 3.2 Principles of Stability for Polycationic Clusters 36 3.3 Synthetic Routes to Polyatomic Cations 37 3.4 Homopolyatomic Cations of the Chalcogens 39 3.4.1 Square-Planar Cations E42+ 39 3.4.2 Prism-Shaped Cations Te64+ and Te62+ 40 3.4.3 Eight-Atomic Molecular Ions E82+ and Te84+ 41 3.4.4 Towards Larger Clusters Chalcogen Polycations with More than Eight Atoms 42 3.5 Homopolyatomic Cations of Bismuth 42 3.6 Heteronuclear Polycationic Clusters of the Heavier Group 15 and 16 Elements 44 3.7 Interactions Between Polycationic Clusters From Weak Association to One-Dimensional Polymers 46 3.8 Summary and Outlook 49 References 50 4 Metal-Catalyzed Dehydrocoupling Routes to Rings, Chains, and Macromolecules based on Elements from Groups 13 and 15 53 Cory A. Jaska and Ian Manners 4.1 Introduction 53 4.2 Thermal Dehydrocoupling of Phosphine-Borane Adducts 54 4.3 Catalytic Dehydrocoupling of Secondary Phosphine-Borane Adducts 54 4.4 Catalytic Dehydrocoupling of Primary Phosphine-Borane Adducts 56 4.5 Thermal Dehydrocoupling of AmineBorane Adducts 57 4.6 Catalytic Dehydrocoupling of Secondary Amine-Borane Adducts 58 4.7 Catalytic Dehydrocoupling of Primary AmineBorane Adducts and NH3BH3 59 4.8 Mechanism of Catalytic Dehydrocoupling of Amine-Borane and Phosphine-Borane Adducts 60 4.9 Application of the Catalytic Dehydrocoupling of Amine-Borane Adducts 62 4.10 Summary 63 References 63 5 Chemistry with Poly- and Perfluorinated Alkoxyaluminates: Gas-Phase Cations in the Condensed Phase? 65 Ingo Krossing and Andreas Reisinger 5.1 Introduction 65 5.2 Available Starting Materials 66 5.3 Weakly Bound Lewis Acid-Base Complexes of the Ag+ Cation 67 5.3.1 Ag(S8) Complexes 68 5.3.2 Complexes with P4S3 69 5.3.3 Complexes with P4 70 5.3.4 Complexes with C2H4 72 5.3.5 Anion Effects 73 5.4 Highly Electrophilic Cations 74 5.4.1 Binary PhosphorusHalogen Cations 74 5.4.2 Simple Carbenium Ions 78 5.5 A Rationalization of the Special Properties of Salts of WCAs Based on Thermodynamic Considerations 80 5.5.1 Stabilization of Weakly Bound Complexes 81 5.5.2 Relative Anion Stabilities Based on Thermodynamic Considerations 82 5.6 Conclusions and Outlook 84 References 85 6 Aluminum(I) Chemistry 89 Herbert W. Roesky 6.1 Introduction 89 6.2 Preparation of Aluminum(I) Halides 89 6.3 Reactions of Aluminum(I) Halides 90 6.4 Chemistry of (Cp*Al)4 (8) 96 6.5 Reactions of [HC(CMeNAr)2]Al (17); Ar=2,6-i-Pr2C6H3 98 6.6 Conclusions 101 References 101 7 Divalent Scandium 105 Gerd Meyer, Liesbet Jongen, Anja-Verena Mudring, and Angela Mller 7.1 Introduction 105 7.2 Synthesis 106 7.3 Scandium Diiodide