Carboranes - 1st Edition - ISBN: 9780123032508, 9780323157582

Carboranes

1st Edition

Authors: Russell Grimes
eBook ISBN: 9780323157582
Imprint: Academic Press
Published Date: 1st January 1970
Page Count: 286
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Description

Carboranes offers a comprehensive treatment of carborane chemistry and covers topics ranging from structures and chemical bonding to the degradation of the icosahedral cage. Carborane polymers as well as small nido- and closo-carboranes, intermediate closo-carboranes, and o-, m-, and p-carboranes are also discussed. This book is comprised of nine chapters and begins with an overview of the chemistry and properties of carboranes. The discussion then turns to the molecular structures of polyhedral carboranes and open-cage carboranes, along with the isomerism and rearrangement of carboranes; nomenclature and numbering systems used for carboranes; and chemical bonding in boranes and carboranes. The following chapters explore the synthesis, reactions, structures, and properties of small nido- and closo-carboranes, intermediate closo-carboranes, and o-, m-, and p-carboranes. The reactions of boranes and alkylboranes with alkynes as well as the degradation of icosahedral carboranes are also described. This monograph will be a useful resource for organic and inorganic chemists.

Table of Contents


Preface

1. Introduction

2. Structures and Bonding

2-1. Structures of the Carboranes

The Polyhedral Carboranes

The Open-Cage Carboranes

Isomerism and Rearrangement

2-2. Nomenclature and Numbering Systems

2-3. Chemical Bonding in the Boranes and Carboranes

The Three-Center Bond

Molecular Orbitals in Boranes and Carboranes

Simplified Molecular Orbital Descriptions

Summary

3. The Small Nido-Carboranes: CB5H9, C2B4H8, C3B3H7, C4B2H6, and C2B3H7

3-1. Structures

3-2. Synthesis

Borane-Alkyne Reactions

Other Routes to Möfo-Carboranes

3-3. Reactions and Properties

2-CB5H9

2,3-C2B4H8

2,3,4-C3B3H7

2,3,4,5-C4B2H6

1,2-C2B3H7

4. The Small Closo-Carboranes: C2B3H5, C2B4H6, C2B5H7, and CB5H7

4-1. Synthesis

Borane-Alkyne Reactions

Conversions of Nido-Carboranes to Closo-Carboranes

Reactions of Alkylboranes with Alkynes

Hydroboration of Alkynylboranes

Dehalogenation of Alkylhaloboranes with Alkali Metals

Pyrolysis and Electric Discharge of Alkylboranes

Reaction of Boranes with Carbon Vapor

4-2. Structures and Properties

C2B3H5

C2B4H6

C2B5H7

CB5H7

5. The Intermediate Closo-Carboranes: C2B6H8, C2B7H9, C2B8H10, and C2B9H11

5-1. Synthesis

Reactions of Boranes with Alkynes

Degradation of Icosahedral Carboranes

5-2. Structures and Properties

C2B6H8

C2B7H9

C2B8H10

C2B9H11

The 1,2-C2B10H12 (o-Carborane) System

6-1. Synthesis, Structure, and Properties

Synthesis

Structure

Thermal Stability and Rearrangement

Chemical Properties

6-2. Alkali Metal and Magnesium Derivatives

Alkali Metal Derivatives

Magnesium Derivatives

Zinc Derivatives

Formation of o-Carborane Dianions in Liquid Ammonia

6-3. Alkyl, Haloalkyl, and Aryl Derivatives

Synthesis

Substitution at Boron

Properties of Alkyl and Haloalkyl Derivatives

Properties of Aryl Derivatives

6-4. Alkenyl and Alkynyl Derivatives

Synthesis of C-Alkenyl Derivatives

Synthesis of B-Alkenyl Derivatives

Synthesis of Alkynyl Derivatives

Reactions of Alkenyl Derivatives

Reactions of Alkynyl Derivatives

6-5. Carboxylic Acids and Esters

Synthesis of C-Substituted Acids and Esters

Synthesis of B-Substituted Acids

Reactions of Acids and Esters

6-6. Alcohols and Ethers

Synthesis of Alcohols

Synthesis of Ethers

Reactions of Alcohols and Ethers

6-7. Aldehydes and Ketones

Synthesis of Aldehydes

Synthesis of Ketones

Reactions of Aldehydes and Ketones

6-8. Nitrogen Derivatives

Nitrates and Related Compounds

Amines, Azides, and Diazonium Salts

Amides

Cyano Derivatives

Other Nitrogen-Containing Derivatives

6-9. Phosphorus, Arsenic, and Antimony Derivatives

6-10. Silicon Derivatives

o-Carboranyl Silanes

o-Carboranyl Alkoxysilanes

6-11. Germanium and Tin Derivatives

6-12. Sulfur Derivatives

6-13. Halogen Derivatives

Electrophilic Halogenation

Photochemical Halogenation

Fluorination

Synthesis of Halo-o-Carboranes from Decaborane(14) Halogen Derivatives

Synthesis of 3-Halo-o-Carboranes

Synthesis of C-Halo-o-Carboranes

Reactions of Halogen Derivatives

6-14. Sigma-Bonded Transition Metal Derivatives

6-15. Mercury Derivatives

7. The 1,7-C2B10H12 and 1,12-C2B10H12 (m- and p-Carborane) Systems

7-1. Comparison of o- and m-Carborane

7-2. Synthesis and Structure of m-Carborane

7-3. Mechanisms of Icosahedral Carborane Rearrangements

ortho-meta and meta-para Isomerizations

The "Reverse Isomerization" of m-Carborane: Conversion of m- to o-Carborane

7-4. Metallation of m-Carborane

7-5. Alkyl, Aryl, and Alkenyl m-Carborane Derivatives

Synthesis

Reactions

7-6. m-Carboranyl Carboxylic Acids and Esters

Synthesis

Reactions

7-7. m-Carboranyl Alcohols and Ethers

Synthesis

Reactions

7-8. m-Carboranyl Aldehydes and Ketones

Reactions

7-9. m-Carboranyl Nitrogen and Phosphorus Derivatives

Nitrates, Amines, and Diazonium Salts

Amides

Phosphorus Derivatives

7-10. m-Carboranyl Silicon Derivatives

7-11. m-Carboranyl Germanium, Tin, and Lead Derivatives

7-12. m-Carboranyl Sulfur Derivatives

7-13. m-Carboranyl Halogen Derivatives

Synthesis from Halo-o-Carboranes

Electrophilic Halogenation

Fluorination

Photochemical Halogenation

C-Halo-m-Carboranes

Reactions and Properties of Halo-m-Carboranes

7-14. m-Carboranyl Mercury Derivatives

7-15. p-Carborane

Synthesis and Structure

Organic and Organometallic Derivatives

Halogen Derivatives

8. Carborane Polymers

8-1. Introduction

8-2. General Considerations

8-3. Class I Polymers

Polyesters

Polyformals

Siloxanes

Polymers with Single Atom Links

Other Class I Polymers

8-4. Class II Polymers

9. Degradation of the Icosahedral Cage. Heteroatom Carboranes and Transition Metal π-Complexes

9-1. Degradation of o- and m-Carborane

C2B9H12- Ions

C2B9H13

C2B9H112- (Dicarbollide) Ions

9-2. Dicarbollide-Boron Insertion Reactions

9-3. The Monocarbon Carborane Anions: CB10H13-, CB10H11-, CB9H10-, CB11nH12-

CB10H13-

CB10H11-

CB9H10- and CB11H12-

9-4. Carboranes Containing Main-Group Cage Heteroatoms

Group II Heteroatoms

Group III Heteroatoms

Group IV Heteroatoms

Group V Heteroatoms

9-5. Carborane-Transition Metal π-Complexes

General Considerations

Dicarbollyl Complexes of Cr, Mo, and W

Dicarbollyl Complexes of Mn and Re

Dicarbollyl Complexes of Fe

Dicarbollyl Complexes of Co

Dicarbollyl Complexes of Ni and Pd

Dicarbollyl Complexes of Cu and Au

Monocarbollyl-Transition Metal π-Complexes

Carbaphosphollyl-Transition Metal π-Complexes

Nonicosahedral-Transition Metal π-Complexes

Supplementary Sources of Information

References

Author Index

Subject Index

Details

No. of pages:
286
Language:
English
Copyright:
© Academic Press 1970
Published:
Imprint:
Academic Press
eBook ISBN:
9780323157582

About the Author

Russell Grimes