The Borane, Carborane, Carbocation Continuum

ISBN-13: 9780471180753 / Angielski / Twarda / 1998 / 438 str.

Joseph Casanova

Opis

A comparative examination of electron-deficient species -from leading researchers in the field. The Borane, Carborane, Carbocation Continuum explores the emerging understanding of the similarities of properties and behavior shared by these electron-deficient species. Based on the work presented at a trailblazing symposium held at the Loker Hydrocarbon Research Institute of the University of Southern California, it brings together the contributions of distinguished scientists from around the world, including Nobel Prize winners George A. Olah and William N. Lipscomb, to illustrate the results of research on the structures and bonding characteristics of boranes, carboranes, and carbocations. As electron-deficient compounds find a place in today's high-field NMR systems and other cutting-edge areas, this unique volume contains important information for advanced students as well as professionals working in organic, inorganic, or physical chemistry, with sections on:

• Patterns of structure in boranes and carboranes -including vertex homogeneity, boron cluster patterns, and seco-systematization of boranes and heteroboranes
• The carborane -carbocation continuum -from boron super-electrophiles and their carbocation analogs to cage systems
• Untangling molecular structures -mechanistic patterns in carborane reactions, advances in metallacarborane sandwich chemistry, and other topics
• New species of boranes and carboranes -such as isoelectronic borane, hydrocarbon, and carbocation metal complexes, and cyclic organohydroborate anions.

Spis treści

Foreword: The The Patternmaker xi
Norman Greenwood

Foreword: A Brief Overview xiii
William N. Lipscomb

Preface xvii
Joseph Casanova

Contributors xix

PART I: PATTERNS OF STRUCTURE IN BORANES AND CARBORANES 1

1 Vertex Homogeneity: The "Hidden Hand" that Governs Electron–Deficient Borane, Carborane, and Carbocation Structures 3
Robert Williams

2 The Borane–Carborane Structural Pattern: Some Correlations and Implications 57
Mark A.Fox and Kenneth Wade

3 Disobedient Skeletons 85
John D. Kennedy

4 Seco–Systematization of Boranes and Heteroboranes 117
Stanislav Hermánek

PART II: THE CARBORANE–CARBOCATION CONTINUUM 129

5 Boron Superelectrophiles and Their Carbocation Analogs 131
George A. Olah

6 Extension of the Borane–Carbocation Continuum to Cage Systems 147
G.K. Surya Prakash, Golam Rasul. Andrei K. Yudin, and Robert E. Williams

7 Are Polyhedral Boranes, Carboranes, and Carbocations Aromatic? 169
Paul von Rague Schleyer and Katayoun Najafian

8 Electron Deficient Compounds and Theory Deficient People 191
Robert W. Parry

PART III: UNTANGLING MOLECULAR STRUCTURES 215

9 Computational Studies of Nido–C4B7H11 Carboranes and Nido–8–Vertex Boranes and Carboranes 217
Joseph W. Bausch and A.J. Tebben

10 Applications of IGLO/GIAO NMR Computations to Carborane Systems: Products of Trimethylamine/Closo–Carborane Reactions; Carborane 13C Chemical Shifts 247
Thomas Onak

11 Mechanistic Patterns in Carborane Reactions as Revealed by ab initio Calculations 259
Michael L. McKee

12 Reactions of Unsaturated Hydrocarbons with Small Boranes: New Insights and Recent Advances 289
Robert Greatrex and Mark A. Fox

13 Recent Advances in Metallacarborane Sandwich Chemistry: Controlled Linking, Stacking, and Cool Fusion 307
Russell N. Grimes

PART IV: NEW SPECIEIS OF BORANES AND CARBORANES 331

14 Isoelectronic Borane and Hydrocarbon Metal Complexes 333
Thomas P. Fehlner

15 Cyclic Organohydroborate Anions: Hydride Transfer Reactions in the Reduction of Metal Carbonyls and Organic Functional Groups; Reactions with Zirconocene and Hafnocene Dichlorides 351
Sheldon G. Shore, Glenn T. Jordan IV, JianPing Liu, Fu–Chen Liu, Edward A. Meyers, Paul L. Gaus

16 Importance of 11B–1H Coupling Constants in Assigning the 11B Signals 367
Stanislav Hermánek, Jan Machacek, Jin Fusek, and Vratislav Blechta

17 Closo–and Nido–Clusters with a B4 or NB3 Skeleton 381
Peter Paetzold

18 New Prespectives in the Chemistry of C2B4– and C4B8–Carboranes 397
Narayan S. Hosmane and John A. Maguire

Index 425

O autorze

JOSEPH CASANOVA, PhD, is Professor of Chemistry Emeritus at the California State University, Los Angeles, and a senior research fellow of the Loker Hydrocarbon Research Institute, University of Southern California.