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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.
Foreword: The The Patternmaker xiNorman Greenwood
Foreword: A Brief Overview xiiiWilliam N. Lipscomb
Preface xviiJoseph 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 3Robert Williams
2 The Borane–Carborane Structural Pattern: Some Correlations and Implications 57Mark A.Fox and Kenneth Wade
3 Disobedient Skeletons 85John D. Kennedy
4 Seco–Systematization of Boranes and Heteroboranes 117Stanislav Hermánek
PART II: THE CARBORANE–CARBOCATION CONTINUUM 129
5 Boron Superelectrophiles and Their Carbocation Analogs 131George A. Olah
6 Extension of the Borane–Carbocation Continuum to Cage Systems 147G.K. Surya Prakash, Golam Rasul. Andrei K. Yudin, and Robert E. Williams
7 Are Polyhedral Boranes, Carboranes, and Carbocations Aromatic? 169Paul von Rague Schleyer and Katayoun Najafian
8 Electron Deficient Compounds and Theory Deficient People 191Robert W. Parry
PART III: UNTANGLING MOLECULAR STRUCTURES 215
9 Computational Studies of Nido–C4B7H11 Carboranes and Nido–8–Vertex Boranes and Carboranes 217Joseph 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 247Thomas Onak
11 Mechanistic Patterns in Carborane Reactions as Revealed by ab initio Calculations 259Michael L. McKee
12 Reactions of Unsaturated Hydrocarbons with Small Boranes: New Insights and Recent Advances 289Robert Greatrex and Mark A. Fox
13 Recent Advances in Metallacarborane Sandwich Chemistry: Controlled Linking, Stacking, and Cool Fusion 307Russell N. Grimes
PART IV: NEW SPECIEIS OF BORANES AND CARBORANES 331
14 Isoelectronic Borane and Hydrocarbon Metal Complexes 333Thomas 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 351Sheldon 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 367Stanislav Hermánek, Jan Machacek, Jin Fusek, and Vratislav Blechta
17 Closo–and Nido–Clusters with a B4 or NB3 Skeleton 381Peter Paetzold
18 New Prespectives in the Chemistry of C2B4– and C4B8–Carboranes 397Narayan S. Hosmane and John A. Maguire
Index 425
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