Inorganic Reactions and Methods

How to use this book Preface to the Series Editorial Consultants to the Series Contributors to Volume 13 6. Formation of the Bonds to Group–IIIB (B, AI, Ga, In, TI) Elements 6.1. Introduction 6.2. Formation of the Group–IIIB–Group–IIIB Element (B, AI, Ga, In, TI) Bond 6.2.1. Introduction 6.2.2. from Group–IIIB Halides 6.2.2.1. by Comproportionation with the Group–IIIB Element or Its Univalent State 6.2.2.2. by Reduction with Metals 6.2.2.3. by Disproportionation of Dinuclear Compounds 6.2.2.4. by Metal Atom and Related Reactions 6.2.3. in Combination with Group–VIB Elements 6.2.4. from Group–IIIB–Group–IVB Bonds 6.2.5. from Gallium in Halogen Acid Media 6.3. Formation of Group–IIIB–Group IA or Group–IIA Bonds 6.4. Formation of Group III–B–Group–IB or Group–IIB Bonds 6.5. Formation of Group–IIIB–Transition– or –Inner Transition–Metal Bonds 6.5.1. Introduction 6.5.2. Formation from Group–IIIB Halides 6.5.2.1. by Reaction with Neutral Metal Bases 6.5.2.2. by Reaction with Anionic Metal Bases 6.5.2.3. by Oxidative–Addition Reactions 6.5.3. Formation from Other Group–IIIB Compounds 6.5.3.1. by Reaction with Neutral Metal Bases 6.5.3.2. by Reaction with Anionic Metal Bases 6.5.3.3. by Oxidative Addition Reactions. 6.5.3.4. by Reaction with Metal Halides 6.6. The Formation of the Group III–Group 0 Element Bond 6.7. Formation of Borides 6.7.1. Introduction 6.7.2. Existence and Crystal Chemistry of Borides 6.7.2.1. Borides with Isolated Boron Atoms 6.7.2.1.1. Metal Frame Structures — Topological Packed Structures. 6.7.2.1.2. Substitutional Metal Borides. 6.7.2.1.3. Metal Boride Structures (Isolated Boron Atoms). 6.7.2.2. Borides with Boron Chains 6.7.2.2.1. Structure Types with Chain Fragments (B 2 , B 3 , B 4 Groups). 6.7.2.2.2. Ternary Borides with Boron–Boron Chain Formation. 6.7.2.3. Borides with Two–Dimensional Boron Networks 6.7.2.4. Borides with Three–Dimensional Boron Networks 6.7.2.4.1. ThB 4 –Type Tetraborides. 6.7.2.4.2. CaB 6 –Type Hexaborides. 6.7.2.4.3. UB 12 –Type Dodecaborides. 6.7.2.4.4. YB 66 –Type Borides. 6.7.2.4.5. Other Types. 6.7.2.4.6. Summary. 6.7.2.5. Solid Solution of Transition and Inner Transition Metals in Boron 6.7.2.5.1. The Solubility in the Various Modifications of Boron. 6.7.2.5.2.Solid Solutions in beta–Rhombohedral Boron. 6.7.2.5.3. Crystallographic Data on Solid Solutions of beta–Rhombohedral Boron. 6.7.3. Preparation of Borides 6.7.3.1. by Direct Combination of the Elements 6.7.3.2. by Reduction of a Metal Compound and Boron Halide with Hydrogen 6.7.3.3. by Fused–Salt Electrolysis 6.7.3.4. by Reduction of a Metal Oxide or Other Metal Compound Using Carbon, Boron or Boron Carbide 6.7.3.5. by Reduction of Boron Oxide or Boron Halides with Metals 6.7.3.6. by Low–Temperature Precipitation of Borides from Solution 6.7.3.7. by Other Methods 6.7.4. Crystal Growth of Borides 6.7.4.1. by Gas–Phase Methods 6.7.4.1.1. by Chemical Vapor Deposition (CVD). 6.7.4.1.2. Crystal Growth of Borides by Chemical Vapor Transport. 6.7.4.2. Liquid–Phase Method 6.7.4.2.1. Crystal Pulling. 6.7.4.2.2. Floating–Zone Technique. 6.7.4.2.3. Flame–Fusion Technique. 6.7.4.3. Flux Methods 6.7.5. Sintering Methods 6.7.5.1. Sintering of Pure Borides 6.7.5.1.1. Comminution of Powders. 6.7.5.1.2. Compacting or Molding of Powders. 6.7.5.1.3. Sintering: Miscellaneous. 6.7.5.1.4. Sintering: Characteristics. 6.7.5.1.5. Sintering of Boride–Metal Composites. 6.7.5.2. Hot Pressing of Pure Borides 6.7.5.2.1. Technology of Hot Pressing. 6.7.5.2.2. Hot–Pressing Characteristics of Pure Borides. 7. Formation of Bonds to the Group–IA (Li, Na, K, Rb, Cs, Fr) or Group–IIA (Be, Mg, Ca, Sr, Ba,Ra) Metals 7.1. Introduction 7.2. Formation of Group–IA (Li, Na, K, Rb, Cs, Fr) or Group–IIA (Be, Mg, Ca, Sr, Ba, Ra)–Group–IA (Li, Na, K, Rb, Cs, Fr) or –Group–IIA (Be, Mg, Ca, Sr, Ba, Ra) Metal Bonds 7.2.1. Introduction 7.2.2. in the Group–IA Elements 7.2.2.1. in Lithium 7.2.2.1.1. Industrial Manufacture. 7.2.2.1.2. The Purity of Commercial Lithium. 7.2.2.1.3. The Purification of Lithium. 7.2.2.1.4. Analysis of Lithium for Impurities. 7.2.2.2. in Sodium 7.2.2.2.1. Industrial Manufacture. 7.2.2.2.2. The Purity of Commercial Sodium. 7.2.2.2.3. The Purification of Sodium. 7.2.2.2.4. Analysis of Sodium for Impurities. 7.2.2.3. in Potassium 7.2.2.3.1. Industrial Manufacture. 7.2.2.3.2. Impurities in Commercial Potassium. 7.2.2.3.3. Purification of Potassium. 7.2.2.3.4. Analysis of Potassium. 7.2.2.4. in Rubidium and Cesium 7.2.2.4.1. Industrial Manufacture. 7.2.2.4.2. Purity of the Commercial Metals. 7.2.2.4.3. Purification. 7.2.2.4.4. Analysis for Impurities. 7.2.2.5. In Francium 7.2.3. in the Group–IIA Elements 7.2.3.1. in Beryllium 7.2.3.1.1. Industrial Manufacture. 7.2.3.1.2. Laboratory Preparation. 7.2.3.1.3. Purity and Purification. 7.2.3.2. in Magnesium 7.2.3.2.1. Industrial Manufacture. 7.2.3.2.2. Laboratory Preparation. 7.2.3.2.3. Purity and Purification. 7.2.3.3. in Calcium 7.2.3.3.1.Industrial Manufacture. 7.2.3.3.2. Laboratory Preparation. 7.2.3.3.3. Purity and Purification. 7.2.3.4. in Strontium and in Barium 7.2.3.4.1. Industrial Manufacture. 7.2.3.4.2. Laboratory Preparation. 7.2.3.4.3. Purity and Purification. 7.2.4. Formation of Alloys Between Group–IA Elements 7.2.4.1. Binary Alloys 7.2.4.1.1. Phase Diagrams. 7.2.4.1.2. Compound Formation. 7.2.4.1.3. Preparations. 7.2.4.2. Multicomponent Alloys 7.2.5. Formation of Alloys Between Group–IIA Elements 7.2.5.1. Binary Alloys 7.2.5.1.1. Phase Diagrams. 7.2.5.1.2. Compound Formation. 7.2.5.1.3. Preparations. 7.2.6. Formation of Alloys Between Group–IA and Group–IA Elements 7.2.6.1. Binary Alloys 7.2.6.1.1. Phase Diagrams. 7.2.6.1.2. Compound Formation. 7.2.6.1.3. Preparations. 7.3. Formation of the Group–IA or –IIA– Group–IB or –IIB Element Bonds 7.3.1. Formation of the Group–IA–Group–IB Element Bonds 7.3.1.1. Phase Diagrams 7.3.1.1.1. Lithium Systems. 7.3.1.1.2. Sodium Systems. 7.3.1.1.3. Potassium Systems. 7.3.1.1.4. Rubidium and Cesium Systems. 7.3.1.2. Compound Formation 7.3.1.3. Preparations 7.3.1.3.1. of Alkali–Metal–Copper Compounds. 7.3.1.3.2. of Alkali–Metal–Silver Compounds. 7.4.1.1. in Metallic Systems 7.4.1.2. in Coordination Compounds Containing a Group–IA – Transition–Metal or Inner–Transition–Metal Bond 7.4.1.2.1. in Synthesis of Compounds Containing Lithium Bonded to a Transition Metal. 7.4.1.2.2. in Synthesis of Compounds Containing Sodium Bonded to a Transition Metal. 7.4.2. Formation of the Group–IIA–and –Inner Transition–Metal Bond 7.4.2.1. in Metallic Systems 7.4.2.2. in Coordination Compounds Containing a Group–IIA – Transition– and Inner–Transition–Metal Bond 7.5. The Formation of the Group IA or IIA–Group 0 Element Bond 8. Formation of the Bond to the Group–IB (Cu, Ag, Au) or –IIB (Zn, Cd, Hg) Elements 8.1. Introduction 8.2. Formation of the Group–IB or –IIB–Group–IB or –IIB Metal Bonds 8.2.1. in Gold Cluster Compounds Containing the Au 3 , Au 4 , Au 5 , Au 6 , Au 7 , Au 8 , Au 9 , Au 11 , Au 13 and Au 55 Cores 8.2.1.1. by Reduction of Au(I) Complexes 8.2.1.2. from Reactions of Evaporated Au with Au(I) Complexes 8.2.1.3. from the Conversion of Clusters 8.2.2. in Other Metal–Metal Bonded Dimers and Clusters of Group–IB Elements 8.2.2.1. Bare Metal Dimers and Clusters 8.2.2.1.1. Metal–Vapor Cryochemistry 1–7 8.2.2.1.2. Other Methods. 8.2.2.2. Dimers and Clusters with Nonbridging Ligands 8.2.2.2.1. Syntheses from Metal Vapors 8.2.2.2.2. Other Methods. 8.2.2.3. Dimers and Clusters with Bridging Ligands 8.2.2.3.1. Compounds of Copper. 8.2.2.3.2. Compounds of Silver. 8.2.2.3.3. Compounds of Gold. 8.2.3. In Univalent Compounds of Zinc and Cadmium 8.2.3.1. Univalent Compounds of Zinc 8.2. Formation of the Group–IB or –IIB–Group–IB or –IIB Metal Bonds 8.2.3.2. Univalent Compounds of Cadmium 8.2.4. in Mercury(I) Compounds from Mercury(II) Compounds 8.2.4.1. Preparation of Simple Mercury(I) Compounds 8.2.4.2. Complexes of Mercury(I) 8.2.4.2.1. Complexes of Mercury(I) with Oxygen–Donor Ligands. 8.2.4.2.2. Complexes of Mercury(I) with Sulfur– and Selenium–Donor Ligands. 8.2.4.2.3. Complexes of Mercury(I) with Nitrogen–Donor Ligands. 8.2.4.2.4. Complexes of Mercury(I) with Phosphorous–, Arsenic– and Antimony–Donor Ligands. 8.2.4.3. Preparation of Organomercury(I) Compounds 8.2.5. Mercury Chain Compounds 8.2.5.1. Mercury Chain Compounds in Liquid SO 2 8.2.5.2. Mercury Chain Compounds in Molten AlCI 3 8.3. Formation of the Group–IB (Cu, Ag, Au) or Group–IIB (Zn, Cd, Hg)– Transition–Metal Bonds 8.3.1. Introduction 8.3.2. Group IB–Transition– and Inner Transition–Metal Bonds 8.3.2.1. by Coupling Carbonyl Anions with Complexes of the Group–IB Monohalides 1 8.3.2.1.1. Formation of Bonds Between Transition Metals and Copper or Silver. 8.3.2.1.2. Formation of Bonds Between Transition Metals and Gold. 8.3.2.2. by Other Methods 8.3.2.2.1. Reaction of Carbonyl Anions with Uncomplexed Derivatives of Group–IB Metals. 8.3.2.2.2. Reaction of Carbonyl Hydrides with Complexes of Group–IB Metals. 8.3.2.2.3. Reactions of Other Transition–Metal Complexes with Group–IB Compounds. 8.3.2.2.4. Codeposition of Group–IB and Transition Metals To Give Bimetallic Clusters. 8.3.2.2.5. Formation of Clusters Containing Group–IB and Transition Metals 1 8.3.3. Synthesis of Group IIB–Transition– and Inner–Transition–Metal Bonds 8.3.3.1. by Reactions of Carbonyl Anions with Divalent Group–IIB Salts 8.3.3.1.1. Derivatives of Zinc and Cadmium. 8.3.3.1.2. Derivatives of Mercury. 8.3.3.2. Reactions of Carbonyls and Substituted Carbonyls with Divalent Group–IIB Salts 8.3.3.2.1. Derivatives of Zinc and Cadmium. 8.3.3.2.2. Derivatives of Mercury. 8.3.3.3. by Reactions of Other Transition–Metal Complexes with Group–IIB Derivatives 8.3.3.4. by Insertion into a Metal–Metal Bond Insertion of a Group–IIB Element into Transition–Metal to Transition–Metal Bonds 8.3.3.5. Other Synthetic Methods 8.3.3.5.1. Reactions of Metals Not Involving Insertion or Exchange. 8.3.3.5.2. Exchange. 8.4. The Formation of the Group–IB or –IIB–Group 0 Element Bond List of Abbreviations Author Index Compound Index Subject Index