Boron Hydrides

by William N. Lipscomb

Overview

In this classic monograph, Nobel Prize–winning chemist William N. Lipscomb elucidates his area of expertise: the general structural principles and reactions of boron hydrides and related compounds. Lipscomb's work appeared only a decade after the structures of boron hydrides were first elucidated and their chemistry formulated into a widely applicable framework. His observations led to a major reconsideration of how atoms bond to form stable molecules.
A concise treatment of the many separate parts of the structural theory and its relation to chemistry, this volume begins with an overview of boron hydrides and related structures, progressing to three-center bonds and their applications, molecular orbitals, nuclear magnetic resonance studies of boron hydrides and related compounds, and reactions of the boron hydrides. More than 120 diagrams and figures illustrate a variety of structures.

Product Details

ISBN-13:	9780486488226
Publisher:	Dover Publications
Publication date:	06/13/2012
Series:	Dover Books on Chemistry Series
Pages:	288
Product dimensions:	5.90(w) x 8.90(h) x 0.60(d)

About the Author

William Nunn Lipscomb, Jr. (1919–2011), a Nobel Prize–winning American inorganic and organic chemist, specialized in nuclear magnetic resonance, theoretical chemistry, boron chemistry, and biochemistry. A student of Linus Pauling, he was a longtime Professor of Chemistry at Harvard University.

Table of Contents

Preface v

Chapter 1 Boron Hydrides and Related Structures 1

1-1 The Hydrides 1

1-2 Negative Ions and Equivalent Coordination 13

1-3 Boron Halides 21

1-4 Structures of the Boronates (Borohydrides) 24

1-5 Carboranes (Heteroatom Hydrides) 25

Chapter 2 Three-Center Bonds and Their Applications 27

2-1 Three-Center Bonds 27

2-2 Basic Assumptions 28

2-3 Three-Center Orbitals 30

2-4 Three-Center Orbitals in the Known Structures 33

2-5 The Equations of Balance 43

2-6 A Topological Theory of Boron Hydrides 49

2-7 Application to Icosahedral Fragments. Neutral Species 53

2-8 Generalization and Resonance Structures of Neutral Compounds 62

2-9 Resonance in B₁₀C₂H₁₂ Structures 73

2-10 Ions of -1 and -2 Charge 75

2-11 Topology of B_aH_bO_c Compounds 77

Chapter 3 Molecular Orbitals 79

3-1 Introduction to Symmetry and Representations. B₅H₉ Framework Orbitals 79

3-2 Energies of Molecular Orbitals 84

3-3 Polyhedral Molecules and Ions 86

3-4 Molecular Orbitals in the Boron Hydrides and Their Ions 105

3-5 Simplified Molecular-Orbital Descriptions 112

3-6 Three-Center and Resonance Descriptions of Polyhedral Species 116

3-7 Borides 117

Chapter 4 Nuclear Magnetic Resonance Studies of Boron Hydrides and Related Compounds 126

4-1 Compounds 127

4-2 Coupling Constants and Chemical Shifts 149

Chapter 5 Reactions of the Boron Hydrides 154

5-1 Summary of Reactions 155

5-2 Structural Features and Reaction Types 164

5-3 The BH₃, BH₄- and BH₅ Units 165

5-4 Reactions of the Bridged BH₂ Group 167

5-5 Reactions of the BH Groups: Halides, Grignard Reagents, Alkyls 171

5-6 Reactions of the BHB Bond 172

5-7 The B-B Bond 172

5-8 Intramolecular Rearrangement of H 173

5-9 Rearrangement of B₅H₈R 175

5-10 Electron Addition to the Boron Framework 175

5-11 Collapse of the Boron Framework 175

5-12 Degradation and Condensation of Boron Frameworks 175

5-13 Loss of H₂ and Polymerization 176

5-14 Chemistry of B₁₀H₁₄ 179

5-15 Chemical Studies of the Carboranes 194

5-16 Concluding Remarks 196

References

Recent Reviews of Boron Chemistry

Appendixes

A Some Three-Center Bond Structures for Ions of -1 and -2 Charges 217

B Spherical Coordinates for Boron Hydride Models 227

Indexes

Name Index 259

Compound Index 265

Subject Index 271