Kooperativer Bibliotheksverbund

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Format: 1 online resource

Edition: 3rd ed.

ISBN: 9780128019054 , 0128019050 , 9780128018941 , 0128018941

Series Statement: Organometallic chemistry

Note: Front Cover -- Carboranes -- Copyright -- Dedication -- Contents -- Preface to the Third Edition -- Preface to the Second Edition -- Chapter 1: Introduction and History -- References -- Chapter 2: Structure and Bonding -- 2.1. General perspective -- 2.2. Nomenclature and numbering -- 2.3. The localized-bond approach -- 2.4. Structural patterns in boron clusters -- 2.5. Extensions of the electron-counting rules -- 2.6. Electron-counting in classically bonded clusters -- 2.7. Isomer stability and cage rearrangement -- 2.8. Cluster aromaticity -- 2.9. ``Electron Deficiency´´ in Polyhedral Boron Clusters -- References -- Chapter 3: Synthesis and Reactivity: An Overview -- 3.1. General preparative routes to carboranes -- 3.1.1. Borane-Alkyne Gas Phase Reactions -- 3.1.2. Borane-Alkyne Reactions in Solution -- 3.1.3. Carborane-Alkyne Reactions -- 3.1.4. Carbon Insertion Via Cyano- and Isocyanoboranes -- 3.1.5. Carboranes from Organoboranes -- 3.2. Interconversion reactions -- 3.2.1. Polyhedral Rearrangement -- 3.2.2. Metal-Promoted Cage Fusion -- 3.2.3. Polyhedral Expansion and Contraction -- 3.3. Substitution at cage carbon and boron atoms -- 3.4. Carboranes as substituents and ligands -- Chapter 4: Small Carboranes: Four- to Six-Vertex Clusters -- 4.1. Overview -- 4.2. 4-Vertex open clusters -- 4.2.1. CB3Hx and C2B2Hx -- 4.3. 5-Vertex open clusters -- 4.3.1. Nido- and Arachno-CB4 Systems -- 4.3.2. Nido-1,2-C2B3H7 -- 4.3.3. Other Open-Cage C2B3 Clusters -- 4.3.4. Nido-C3B2 Clusters -- 4.4. 5-Vertex closo clusters -- 4.4.1. CB4Hx -- 4.4.2. 1,5-C2B3H5 -- 4.4.2.1. Synthesis -- 4.4.2.2. Structure and Bonding -- 4.4.2.3. Physical Properties and Reactivity -- 4.4.3. Closo-C3B2H5+ -- 4.5. 6-Vertex open clusters -- 4.5.1. Nido-2-CB5H9 -- 4.5.1.1. Synthesis -- 4.5.1.2. Structure and Properties -- 4.5.2. Hypho-CB5H13 -- 4.5.3. Nido-2,3-C2B4H8. , 4.5.3.1. Synthesis -- 4.5.3.2. Structure and Properties -- 4.5.4. Nido-2,4-C2B4H8 -- 4.5.4.1. Synthesis -- 4.5.4.2. Structure and Properties -- 4.5.5. Arachno- and Hypho-C2B4Hx Clusters -- 4.5.6. Nido-2,3,4-C3B3H7 -- 4.5.6.1. Synthesis -- 4.5.6.2. Structure and Properties -- 4.5.7. Nido-2,3,5-C3B3H7 -- 4.5.7.1. Synthesis -- 4.5.7.2. Structure and Properties -- 4.5.8. Nido-2,3,4,5-C4B2H6 -- 4.5.8.1. Synthesis -- 4.5.8.2. Structure and Properties -- 4.5.9. Nido-2,3,4,5,6-C5BH6+ -- 4.5.9.1. Synthesis -- 4.5.9.2. Structure and Properties -- 4.6. 6-Vertex closo clusters -- 4.6.1. 1-CB5H7 and 1-CB5H6- -- 4.6.1.1. Synthesis -- 4.6.1.2. Structure and Properties -- 4.6.2. 1,2- and 1,6-C2B4H6 -- 4.6.2.1. Synthesis -- 4.6.2.2. Structure and Physical Properties -- 4.6.2.3. Reactions of Closo-1,2-C2B4 Clusters -- 4.6.2.4. Reactions of Closo-1,6-C2B4 Clusters: Hydrolysis, Methanolysis, and Oxidation -- 4.6.2.5. Polyhedral Expansion -- 4.6.2.6. Cage Linkage -- 4.6.2.7. Introduction of Substituents -- References -- Chapter 5: Intermediate Carboranes: Seven- to Nine-Vertex Clusters -- 5.1. Overview -- 5.2. 7-Vertex open clusters -- 5.2.1. Nido-C2B5H8- -- 5.3. 7-Vertex closo clusters -- 5.3.1. 2-CB6H7- -- 5.3.2. 2,3-C2B5H7 -- 5.3.3. 2,4-C2B5H7 -- 5.3.3.1. Synthesis -- 5.3.3.2. Structure and Electronic Properties -- 5.3.3.3. Substitution at Carbon -- 5.3.3.4. Substitution at Boron: Halogenation -- 5.3.3.5. B-Alkylation and -Alkenylation -- 5.3.3.6. Photochemical B-Substitution -- 5.3.3.7. Cage Rearrangement in Substituted Derivatives -- 5.3.3.8. Cage Opening and Polyhedral Expansion -- 5.3.3.9. Cage Coupling -- 5.3.4. C3B4 Clusters -- 5.4. 8-Vertex open clusters -- 5.4.1. Arachno-CB7H13 and CB7H12- -- 5.4.2. Nido-C2B6H10 -- 5.4.3. Nido-C2B6H82- -- 5.4.4. Arachno-C2B6H12 -- 5.4.5. Hypho-C2B6H13- -- 5.4.6. Nido-C3B5H9 -- 5.4.7. Nido-C4B4H8 -- 5.4.7.1. Synthesis. , 5.4.7.2. Structure and Properties -- 5.5. 8-Vertex closo clusters -- 5.5.1. CB7H8- -- 5.5.1.1. Synthesis -- 5.5.1.2. Structure -- 5.5.2. 1,7-C2B6H8 -- 5.5.2.1. Synthesis -- 5.5.2.2. Structure and Properties -- 5.6. 9-Vertex open clusters -- 5.6.1. Nido-CB8H12, arachno-CB8H14, and arachno-CB8H13- -- 5.6.1.1. Synthesis -- 5.6.1.2. Structure and Properties -- 5.6.2. Nido-C2B7H11 -- 5.6.3. Arachno-C2B7H13 -- 5.6.3.1. Synthesis -- 5.6.3.2. Structure and Properties of 6,8-C2B7H13 -- 5.6.3.3. Structure and Properties of 6,7-C2B7H13 -- 5.6.4. Hypho-C3B6H13- -- 5.7. 9-Vertex closo clusters -- 5.7.1. 4-CB8H9- -- 5.7.1.1. Synthesis -- 5.7.1.2. Structure and Properties -- 5.7.2. 4,5-C2B7H9 -- 5.7.2.1. Synthesis -- 5.7.2.2. Structure and Properties -- References -- Chapter 6: Ten-Vertex Carboranes -- 6.1. Overview -- 6.2. 10-Vertex open clusters -- 6.2.1. Nido-CB9H12- and Arachno-CB9H14- -- 6.2.1.1. Synthesis -- 6.2.1.2. Structure and Properties -- 6.2.2. Nido-C2B8H12 -- 6.2.2.1. Synthesis -- 6.2.2.2. Structure -- 6.2.2.3. Deprotonation and Heteroatom Insertion -- 6.2.2.4. Introduction of Substituents -- 6.2.2.5. Cage Rearrangement and Conversion to Other Cluster Systems -- 6.2.3. Arachno-C2B8H14 -- 6.2.3.1. Synthesis -- 6.2.3.2. Structure -- 6.2.3.3. Introduction of Substituents -- 6.2.3.4. Enantiomeric Resolution and Circular Dichroism -- 6.2.4. Nido-C3B7H11 and Arachno-C3B7H13 -- 6.2.4.1. Synthesis -- 6.2.4.2. Structure and Properties -- 6.2.5. Nido-C4B6H10 -- 6.2.5.1. Synthesis -- 6.2.5.2. Structure and Properties -- 6.2.6. Arachno-C4B6H12 -- 6.3. 10-Vertex closo clusters -- 6.3.1. 1- and 2-CB9H10- -- 6.3.1.1. Synthesis -- 6.3.1.2. Structure and Properties -- 6.3.1.3. Introduction of Substituents: Deuteration and Halogenation -- 6.3.1.4. Introduction of Alkyl, Amino, and Other Organic Groups -- 6.3.1.5. Transition-Metal Complexes -- 6.3.2. C2B8H10. , 6.3.2.1. Synthesis of Closo-1,6-C2B8 clusters -- 6.3.2.2. Synthesis of Closo-1,2-C2B8 Clusters -- 6.3.2.3. Synthesis of Closo-1,10-C2B8 Clusters -- 6.3.2.4. Structures of C2B8H10 Isomers -- 6.3.2.5. Electronic Properties and Cage Rearrangement -- 6.3.2.6. Introduction of Substituents on Carbon -- 6.3.2.7. Introduction of Substituents on Boron -- 6.3.2.8. Cage Expansion and Degradation -- References -- Chapter 7: Eleven-Vertex Carboranes -- 7.1. Overview -- 7.2. 11-Vertex open clusters -- 7.2.1. Nido-CB10H13- -- 7.2.1.1. Synthesis -- 7.2.1.2. Structure -- 7.2.1.3. Substitution at Boron: General Methods -- 7.2.1.4. Halogenation -- 7.2.1.5. Introduction of Other Functional Groups -- 7.2.1.6. Carbon- and Phosphorus-Bridged Nido-CB10 Clusters -- 7.2.1.7. Cage Expansion Reactions -- 7.2.1.8. Polymerization -- 7.2.2. Nido-C2B9H13, Nido-C2B9H12-, and Nido-C2B9H112- -- 7.2.2.1. Controlled Deboronation of C2B10 Carboranes -- 7.2.2.2. Direct Synthesis of Nido-7,8-C2B9H12- from B10H14 or B10H13- -- 7.2.2.3. Synthesis of Nido-7,9-C2B9H12- Derivatives from Closo-C2B9H11 -- 7.2.2.4. Synthesis of Nido-C2B9H13 Isomers -- 7.2.2.5. Synthesis of Nido-C2B9H112- (Dicarbollide) Anions -- 7.2.2.6. Structural Studies of Nido-C2B9 Cage Systems -- 7.2.2.7. Introduction of Substituents: Halogenation and Deuteration -- 7.2.2.8. Alkylation, Protonation, and Cage Rearrangement -- 7.2.2.9. Introduction of Functional Groups of the Main-Group Elements -- 7.2.2.10. Dimers and Multicage Derivatives -- 7.2.2.11. Transition Metal Complexes -- 7.2.2.12. Reboronation -- 7.2.2.13. Other Properties of Nido-C2B9 Carboranes -- 7.2.3. Nido-C3B8H12 and Nido-C3B8H11- -- 7.2.3.1. Synthesis -- 7.2.3.2. Cage Isomerization -- 7.2.3.3. Structures and Reactions -- 7.2.3.4. Hypho-C3B8H15- -- 7.2.4. Nido-C4B7H11 -- 7.2.4.1. Synthesis -- 7.2.5. Arachno-C4B7H13 -- 7.2.5.1. Synthesis. , 7.3. 11-Vertex closo clusters -- 7.3.1. Closo-CB10H11- -- 7.3.1.1. Synthesis -- 7.3.1.2. Structure -- 7.3.2. Closo-C2B9H11 -- 7.3.2.1. Synthesis -- 7.3.2.2. Structure -- 7.3.2.3. Cage Isomerization -- 7.3.2.4. Cage Opening -- 7.3.2.5. Substitution at Boron -- References -- Chapter 8: Icosahedral Carboranes: Closo-CB11 Clusters -- 8.1. Overview -- 8.2. Synthesis and structure -- 8.2.1. Parent CB11H12- -- 8.2.2. Substitution at Carbon -- 8.2.3. Substitution at Boron by Electrophilic Reagents -- 8.2.4. Synthesis of B-Substituted Derivatives via Boron Insertion -- 8.2.5. Polyhalogenation at Boron -- 8.2.6. Polyalkylation at Boron -- 8.2.7. Mixed Alkyl-Halo Derivatives -- 8.2.8. Acid-Base Properties -- 8.2.9. Metal Complexation -- 8.2.10. Special Properties of CB11Me12-, HCB11Me11-, and CB11Me12 -- References -- Chapter 9: Icosahedral Carboranes: 1,2-C2B10H12 -- 9.1. Overview -- 9.2. Synthesis of the 1,2-C2B10 cage -- 9.2.1. From B10H14 -- 9.2.2. From BH4- and B10H102- Salts -- 9.2.3. Boron Addition to 11-Vertex Nido-Carboranes -- 9.2.4. Other o-Carborane-Forming Reactions -- 9.3. Structure and properties -- 9.4. Substitution at carbon -- 9.4.1. Metallation with Group 1 and 2 Metals -- 9.4.2. Substitution via C-Metallated Carboranes -- 9.4.2.1. Addition of Boron at Carbon -- 9.4.2.2. Addition of Aluminum, Gallium, Indium, and Thallium at Carbon -- 9.4.2.3. Addition of Silicon, Germanium, Tin, and Lead at Carbon -- 9.4.2.4. Addition of Nitrogen, Phosphorus, Arsenic, Antimony, and Bismuth at Carbon -- 9.4.2.5. Addition of Oxygen at Carbon -- 9.4.2.6. Addition of Sulfur, Selenium, and Tellurium at Carbon -- 9.4.2.7. Addition of Halogens at Carbon -- 9.4.2.8. Addition of Zinc and Mercury at Carbon -- 9.4.2.9. Addition of Transition Metals at Carbon -- 9.4.2.10. Addition of Lanthanide Series Metals at Carbon -- 9.4.2.11. Organosubstitution at Carbon. , 9.4.3. Substitution at Carbon without Metallation.

Language: English