About the Book
For the first time, the discipline of modern inorganic chemistry has been systematized according to a plan constructed by a council of editorial advisors and consultants, among them are three Nobel laureates (E. O. Fischer, H. Taube and G. Wilkinson). Rather than producing a collection of unrelated review articles, the series creates a framework, which reflects the creative potential of this scientific discipline. Thus, it stimulates future development by identifiying areas which are fruitful for further research. The work is indexed in a unique way by a structured system which maximizes its usefulness to the reader. It augments the organization of the work by providing additional routes of access for specific compounds, reactions and other topics.
Table of Contents:
How to Use this Book Preface to the Series Editorial Consultants to the Series Contributors to Volume 10 5. The Formation of Bonds to the Group IVB Elements (C, Si, Ge, Sn, Pb) (Part 2) 5.3 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIIB (B, Al, Ga, In, Tl) 5.3.1. Introduction 5.3.2. Formation of Carbon - Boron Bonds 5.3.2.1. Industrial Preparation of Boron Carbide. 5.3.2.1.1. Industrial Preparation of Boron Carbide Powders. 5.3.2.1.2. Densification of Powders. 5.3.2.2. Laboratory Preparation of Boron Carbide (from the Elements or Boron Halides) 5.3.2.2.1. by Direct Synthesis. 5.3.2.2.2. by Reduction of BCl3 by H2 in the Presence of Carbon. 5.3.2.2.3. by Chemical Vapor Deposition (CVD). 5.3.2.2.4. by Reduction of Boric Anhydride at Low Temperatures. 5.3.2.2.5. by Plasma Synthesis. 5.3.2.2.6. by Physical Vapor Deposition (PVD). 5.3.2.2.7. Crystal Growth. 5.3.2.2.8. Boron Carbide Fibers. 5.3.2.3. from Boron Halides 5.3 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIIB (B, Al, Ga, In, Tl) 5.3.2.3.1. by Reaction with More Polar Organometallics (Metal Metal Exchange, Excluding Amino , Oxo and Thioboron Halides). 5.3.2.3.2. by Reaction with an Organoboron Active Metal Reagent. 5.3.2.3.3. by Substitution of Hydrocarbons. 5.3.2.3.4. by Addition to Olefinic and Acetylenic Linkages (Haloboration). 5.3.2.3.5. by Reaction with Diazoalkanes. 5.3.2.3.6. by Redistribution Reactions with Organoboranes. 5.3.2.4. from Boron Alkoxides with More Polar Organometallics 5.3.2.4.1. Alkyl and Arylboronic Acids. 5.3.2.4.2. Alkyl and Arylborinic Acids. 5.3.2.4.3. to form Organoboranes with Three B - C Bonds. 5.3.2.5. from Boron Hyrides 5.3.2.5.1. by Addition to Olefins and Acetylenes (Hydroboration). 5.3.2.5.2. by Addition to Polar Organometallics to Form Organoborates. 5.3.2.5.3. by Redistribution of Organoboron Hydrides. 5.3.2.6. from Organoboranes 5.3.2.6.1. by Redistribution. 5.3.2.6.2. by Isomerization and Displacement. 5.3.2.6.3. by Pyrolytic Elimination of H2. 5.3.2.6.4. by Addition of Olefinic and Acetylenic Linkages (Carboboration). 5.3.2.7. from Larger Boranes and Carboranes 5.3.2.7.1. by Hydroboration of a Polyborane. 5.3.2.7.2. by Modified Metal Halide Catalyzed Alkylations with Organic Halides at a Boron Site. 5.3.2.7.3. by B,B Addition of Polyboranes to Alkynes. 5.3.2.7.4. by Boron Hydrides with Acetylides, Cyanides, or Isocyanides. 5.3.2.7.5. by CO Displacements from Polyboranes. 5.3.2.7.6. by Other Reactions Using Polyboranes. 5.3.3. Formation of Carbon - Al Bonds 5.3.3.1. from the Elements 5.3.3.2. from Al Metal and Its Alloys 5.3.3.2.1. by the Interaction of H2, Olefin and Al Metal. 5.3.3.2.2. by the Action of Organic Halides on Al. 5.3.3.2.3. by the Reaction of Organomercurials with Al. 5.3.3.3. from Al Halides or Organoaluminum Halides 5.3.3.3.1. by Reaction with Polar Organometallics. 5.3.3.3.2. by Redistribution with Organoaluminums. 5.3.3.3.3. by the Interaction with an Active Metal Hydride and Olefin. 5.3.3.3.4. by the Dehalogenation of RnAlX3 n with Active Metals. 5.3.3.4. from Al Hydrides or Complex Al Hydrides 5.3.3.4.1. by Addition to Olefins or Acetylenes (Hydroalumination). 5.3.3.4.2. by Transfer of Al Hydride from One Olefin to Another Al Alkyl Olefin Displacement. 5.3.3.4.3. by Redistribution with Organoaluminums. 5.3.3.4.4. by Exchange with Other Organometallics. 5.3.3.5. from Other Organoaluminum Compounds 5.3.3.5.1. by Addition of R - Al Bonds to Olefins or Acetylenes (Carbalumination). 5.3.3.5.2. by Substitution of Acidic Carbon - Hydrogen Bonds by Carbon - Al Bonds (Alumination). 5.3.3.5.3. by Thermal Elimination from R3Al to Yield Olefin and R'3Al (Thermal Degradation). 5.3 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIIB (B, Al, Ga, In, Tl) 5.3.3.5.4. by Exchange of Organic Groups Between Organoaluminum and Other Organometallics (Transmetallation). 5.3.3.5.5. by Reaction with Diazo Compounds. 5.3.4. Formation of Carbon - Ga Bonds 5.3.4.1. from the Elements 5.3.4.2. from Gallium Metal and Its Alloys 5.3.4.2.1. by the Action of Organic Halides. 5.3.4.2.2. by the Action of Organic Halides on Ga Mg Alloy or Mixtures of Ga and Mg Metals. 5.3.4.2.3. by Organomercurials with Ga Metal. 5.3.4.2.4. by Electrolysis of Organoalanes at a Ga Anode. 5.3.4.2.5. by Electrolysis of Organic Halides at a Ga Cathode. 5.3.4.3. from Ga or Organogallium Halides 5.3.4.3.1. with Other Organometallics. 5.3.4.3.2. by Cleavage of Siloxane Bridges. 5.3.4.3.3. with Low Oxidation State Ga Halides. 5.3.4.3.4. by Reaction with Diazomethane. 5.3.4.3.5. by Redistribution with Organogallanes. 5.3.4.4. from Ga Hydrides or Organogallium Hydrides 5.3.4.4.1. by Addition to Olefins or Acetylenes. 5.3.4.4.2. by Transfer of Ga Hydride from One Olefin to Another: Alkylgallium Olefin Displacement. 5.3.4.5. from Other Organogallium Compounds or to Acetylenes 5.3.4.5.1. by Substitution of Carbon - Hydrogen for Carbon - Ga Bonds (Galliation). 5.3.4.5.2. by Exchange of Organic Groups between Organogallanes and Other Organometallics. 5.3.4.5.3. by Reaction with Nitriles and Cyanide Ion. 5.3.4.5.4. giving Tetraalkylgallate Anions. 5.3.5. Formation of the Carbon - In Bond 5.3.5.1. from the Elements 5.3.5.2. from In Metal and Its Alloys 5.3.5.2.1. by the Action of Organic Halides. 5.3.5.2.2. by the Action of Organic Halides on Highly Reactive in Metal. 5.3.5.2.3. by the Action of Organic Halides with In Mg Alloy or a Mixture of In and Mg Metals. 5.3.5.2.4. by Reaction of Cyclopentadiene with In Vapor. 5.3.5.2.5. by the Action of Organomercurials on In Metal. 5.3.5.2.6. by Organothallium Compound with In Metal. 5.3.5.2.7. by Electrolysis of Organoalanes at an In Anode. 5.3.5.2.8. by Electrolysis of Organic Halides at an In Cathode. 5.3.5.3. from In Halides or Organoindium Halides 5.3.5.3.1. with More Polar Organometallics. 5.3.5.3.2. by Redistribution with Organoindiums. 5.3.5.3.3. by the Oxidative Insertion of In(I) Halide into an Alkyl Halide Bond. 5.3.5.3.4. by Oxidative Arylation of In(I) Halides by Arylmercurials. 5.3.5.4. from other Organoindiums 5.3.5.4.1. by Transfer of In Hydride from One Olefin to Another: Indium Alkyl Olefin Displacement. 5.3.5.4.2. by Substitution of Acidic Carbon - Hydrogen bonds by Carbon - In Bonds (Indiation). 5.3.6. Formation of Carbon - Tl Bonds 5.3.6.1. from the Elements 5.3.6.2. from Tl Metal and Its Alloys 5.3.6.2.1. by the Action of Organic Halides. 5.3.6.2.2. by Reaction of Cyclopentadiene with Tl Vapor. 5.3.6.2.3. by Pyrolysis of Hydrocarbons. 5.3.6.2.4. by the Action of Diarylhalonium Fluoroborates. 5.3 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIIB (B, Al, Ga, In, Tl) 5.3.6.2.5. by the Decomposition of Aryldiazonium Fluoroborates. 5.3.6.2.6. by Action of Organomercurials. 5.3.6.2.7. by Action of InC5H5 h1. 5.3.6.2.8. by Electrolysis of Organoalanes at a Tl Anode. 5.3.6.2.9. by Electrolysis of Organic Halides at a Tl Cathode. 5.3.6.3. from Tl(I) or Tl(III) Salts or Organothallium (III) Halides 5.3.6.3.1. with More Active Organometallics. 5.3.6.3.2. by Action of Tl(I) Halide with an Active Organometallic and an Organic Halide. 5.3.6.3.3. with an Organoboronic Acid. 5.3.6.3.4. by Substitution of Acidic C - H Bonds by C - Tl Bonds (Thallation). 5.3.6.3.5. by Addition of Tl(III) Salts to Olefins (Oxythallation). 5.3.6.3.6. by Reaction with Diazoalkanes. 5.3.6.3.7. by Redistribution. 5.3.6.3.8. by Reaction with Organo Derivative of Hg, Sn, Pb and Bl. 5.3.6.3.9. by Decarboxylation or Desulfination. 5.3.6.4. from Other Organothalliums 5.3.6.4.1. by Substitution of Acidic Carbon - Hydrogen Bonds by Carbon - Tl Bonds. 5.3.6.4.2. by Exchange with Organolithiums. 5.3.7. Formation of Si - Boron Bonds 5.3.7.1. from the Elements 5.3.7.2. from Dihalosilylenes by Boron Halides. 5.3.7.3. from Silicon Halides 5.3.7.3.1. with Haloboranes and Potassium Metal. 5.3.7.3.2. with Boron Hydride Anions. 5.3.7.4. from Silyl Alkali Metal Reagents 5.3.7.4.1. with Haloaminoboranes and Haloborazines and Haloboranes. 5.3.7.4.2. with Organoboranes. 5.3.7.4.3. with Alkoxyboranes. 5.3.8. Formation of Si - Al Bonds 5.3.8.1. from the Elements 5.3.8.2. from Silyl Alkali Metal Reagents 5.3.8.2.1. with Organoaluminum Halides. 5.3.8.2.2. with Lithium Aluminum Hydride or Aluminum Hydride. 5.3.8.3. from Bis(silyl)mercurials with Al Metal 5.3.8.4. from Organosilicon Halides with Al Metal 5.3.8.5. from Tris(trimethylsilyl)aluminum with Bis(trimethylsilyl)mercury and an Alkali Metal 5.3.8.6. from Alkali Tetrakis(trimethylsilyl)aluminate with Al Chloride 5.3.8.7. from Disilanes or Polysilanes with LIAlH4 5.3.9. Formation of the Si - Ga Bond 5.3.10. Formation of the Si - In Bond 5.3.11. Formation of the Si - Tl Bond 5.3.11.1. from Organosilicon Hydrides with Trialkyl Thallium 5.3.11.2. from Bis(silyl)mercurials with Trialkyl Thallium 5.3.12. Formation of the Ge - Boron Bond 5.3.12.1. from the Elements 5.3.12.2. from Germyl Alkali Metal Reagents 5.3.12.2.1. with Haloaminoboranes and Haloborazines. 5.3.12.2.2. with Triorganoboranes. 5.3.12.3. from Ge Halides and Boron Hydride Anions 5.3.13. Formation of the Ge - Al Bond 5.3.13.1. from the Elements 5.3.13.2. from Bis(germyl)mercurials with Al Metal 5.3.13.3. from Germyl Alkali Metal Reagent with Lithium Aluminum Hydride 5.3.13.4. from Aryldigermanes by Reaction with Lithium Aluminum Hydride 5.3.13.5. from Ge Halides or Organogermanium Halides with Al Alkyls 5.3 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIIB (B, Al, Ga, In, Tl) 5.3.14. Formation of the Ge - Ga Bond 5.3.15. Formation of the Ge - In Bond 5.3.16. Formation of the Ge - Tl Bond 5.3.17. Formation of the Sn - Boron Bond 5.3.17.1 from the Elements 5.3.17.2 from Stannyl Alkali Metal Reagents 5.3.17.2.1. with Trialkylboranes. 5.3.17.2.2. with Haloaminoboranes. 5.3.17.3. from Tin Halides 5.3.17.3.1. with Boron Co Compounds. 5.3.17.3.2. with Boron Hydride Anions. 5.3.17.3.3. with Boron Heterocycles. 5.3.17.4. Utilizing Stannylenes as Electron Pair Donor Bases. 5.3.18. Formation of the Sn - Al Bond 5.3.18.1. from the Elements 5.3.18.2. from Bis(stannyl)mercurials with Al Metal 5.3.18.3. from Stannyl Alkali Metal Reagents with Al Alkyls 5.3.18.4. from Sn(II) Halides with Al Alkyls 5.3.19. Formation of the Sn - Ga Bond 5.3.20. Formation of the Sn - In Bond 5.3.21. The Formation of the Sn - TI Bond 5.3.21.1. from Organotin Hydrides with Organothalliums 5.3.21.2. from Stannyl Alkali Metal Reagents with Tl Alkyls 5.3.21.3. from Organodistannanes with LI Tetramethylthallate 5.3.22. Formation of the Pb - Boron Bond 5.3.22.1. from the Elements 5.3.22.2. from Plumbyl Alkali Metal Reagents with Haloaminoboranes 5.3.22.3. from Lead Halides 5.3.22.3.1. with Organoboron Co Compounds. 5.3.22.3.2. with Borane and Carborane Anions 5.3.22.4. from Lead(II) Acetate and Carborane Aions 5.4 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIA (Be, Mg, Ca, St, Ba, Ra) 5.4.1. Introduction 5.4.2. Formation of the Carbon - Mg Bond. 5.4.2.1. from the Elements 5.4.2.2. from Mg Metal and its Alloys 5.4.2.2.1. by Action of Organic Halides or Other Derivatives on the Metal. 5.4.2.2.2. from Organomercury Compounds with the Metal. 5.4.2.2.3. from the Action of Stable Free Radicals on the Metal. 5.4.2.2.4. from the Formation of Adducts Between Conjugated Hydrocarbons and the Metal in the Presence of Donor Solvents. 5.4.2.2.5. from Acidic Hydrocarbons to Evolve H2. 5.4.2.3. from Magnesium Halides 5.4.2.3.1. by Reaction with Group IA Organometallics. 5.4.2.3.2. by Redistribution with Diorganomagnesium. 5.4.2.3.3. by the Combined Action of Mg Metal and its Halides on Certain Organic Radicals or Conjugated Hydrocarbons. 5.4.2.4. from Magnesium Hydride 5.4.2.4.1. by Addition to Olefinic or Acetylenic Linkages. 5.4.2.4.2. with Acidic Hydrocarbons to Evolve H2 5.4.2.4.3. with Organometallic Compounds. 5.4.2.5. from Other Organomagnesium Derivatives 5.4.2.5.1. by Addition to Alkene or Alkyne Functions: Carbomagnesiation. 5.4.2.5.2. by Metallation of Acidic Hydrocarbons. 5.4.2.5.3. by Transfer of the Elements of Magnesium Hydride to Alkenes, Especially with Catalysis by Tl Compounds. 5.4 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIA (Be, Mg, Ca, St, Ba, Ra) 5.4.3. Formation of the Carbon - Group IIA Element Bond (Except Mg) 5.4.3.1. from the Elements 5.4.3.2. from the Group IIA Metals and Their Alloys 5.4.3.2.1. by Organic Halides with the Metal 5.4.3.2.2. by Organomercury, Organocadmium or Organozinc Compounds with the Metal. 5.4.3.2.3. by Acidic Hydrocarbons with the Metal to Evolve H2. 5.4.3.3. from Group IIA Halides and Related Compounds 5.4.3.3.1. with More Active Organometallics. 5.4.3.3.2. by Redistribution with its Diorganometallic Derivative. 5.4.3.4. from Other Group IIA Organometallics of the Same Metal 5.4.3.4.1. by Addition to Olefinic or Acetylenic Derivatives. 5.4.3.4.2. with Acidic Hydrocarbons to Evolve RH. 5.4.3.4.3. by Transfer of Metal Hydride to Olefinic or Acetylenic Derivatives. 5.4.3.4.4. by Reaction with Other Organometallics. 5.4.4. Formation of the Si - Group IIA Element Bond 5.4.4.1. from the Elements 5.4.4.2. from Organohalosilanes with a Group IIA Branched Metal Organic Reagent 5.4.4.3. from Organohalosilanes with Mg Metal 5.4.4.4. from Bis(silyl)mercurials with Mg Metal 5.4.4.5. from an Organosilyl Transition Metal Complex with an Organomagnesium Halide Reagent 5.4.4.6. from Hexaphenyldisilane with a Group IIA Metal 5.4.4.7. from Organosilyllithium with an Organomagnesium Halide Reagent 5.4.5. The Formation of the Germanium - Group IIA Element Bond 5.4.5.1. from the Elements 5.4.5.2. from Ge Halides or Organogermanium Halides with a Group IIA Metal or Organomagnesium Halide Reagent 5.4.5.3. by Transfer of the Elements of Magnesium Hydride to Alkenes, Especially with Catalysis by Tl Compounds. 5.4.5.4. from a Triphenylgermyl Transition Metal Complex with an Organomagnesium Halide Reagent 5.4.5.5. from Bis(germyl)mercurials with Mg Metal 5.4.5.6. from Hexaaryldigermanes with Mg, Ca, Sr, Ba 5.4.6. Formation of the Tin - Group IIA Element Bond 5.4.6.1. from the Elements 5.4.6.2. from Organotin Halides by Reaction with Metallic Magnesium 5.4.6.3. from Hexaorganodistannanes with Mg Metal 5.4.6.4. from Hexaorganodistannanes with Organomagnesium Halide Reagents 5.4.6.5. from Organotin Hydrides with Organomagnesium Halide Reagents 5.4.6.6. from Sn(II) Compounds with Organomagnesium Halide Reagents 5.4.6.7. from Stannyl Alkali Metal Reagents with Organomagnesium Halide Reagents 5.4.7. Formation of the Lead - Group IIA Bond 5.4.7.1. Lead Group IIA Alloys and Intermetallic Compounds 5.4.7.1.1. from the Elements. 5.4.7.1.2. by Reduction. 5.4.7.1.3. by Electrolysis. 5.4.7.2. Formation of Organolead Group IIA Compounds 5.4.7.2.1. from Hexaorganodileads with a Group IIA Metal. 5.4.7.2.2. from Hexaorganodileads with Organomagnesium Halide Reagents. 5.4 Formation of Bonds between Elements of Group IVB (C, Si, Ge, Sn, Pb) and Group IIA (Be, Mg, Ca, St, Ba, Ra) 5.4.7.2.3. from Tetraorganoleads with a Group IIA Metal. 5.4.7.2.4. from Organolead Halides with a Group IIA Metal. 5.4.7.2.5. from Lead(II) Halides with Organomagnesium Halide Reagents. List of Abbreviations Author Index Compound Index Subject Index
