Organometallic Reaction Mechanisms of the Nontransition Elements provides selected significant developments in organometallic reaction mechanisms and outlines a self-consistent set of interpretations of these mechanisms. This book is organized into eight chapters and begins with discussions on bonding in theoretically important types of organometallic compounds and the potential surfaces and their relation to mechanisms. This is followed by significant chapters on electrophilic displacement reactions. Polar 1,2-addition and elimination reactions are covered in a separate chapter. Radical and photochemical reactions are described in the concluding chapters of the book, including the reverse reaction involving incorporation of a free metal and an organic halide into an organometallic compound. Organic chemists and researchers will find this book invaluable.
Inhalt
Preface
Chapter 1 Bonding, Structure, and Potential Energy Surfaces
I. Introduction
II. Carbon-Metal Bonds
III. Three-Center Bonds
IV. Potential Energy Surfaces
References
Chapter 2 Electrophilic Displacement: NMR Studies of Metal Exchange
I. Introduction
II. Principles of NMR Line Broadening
II. Group III
IV. Group II
V. Lithium
VI. Group IV
References
Chapter 3 Electrophilic Displacement: Replacements of Metal Cations
I. Transition State Models
II. Mercury(II) Electrophiles
III. Halogen Electrophiles
IV. The Proton as Electrophile or Electrofuge
V. Group IV and V Electrophiles with Grignard and Related Reagents
References
Chapter 4 Electrophilic Displacement Involving Neighboring Sites
I. Introduction
II. Migrations to Electron-Deficient Oxygen or Nitrogen
III. Migrations to Electron-Deficient Carbon
IV. Migrations of Group VI and VII Anions from Boron to Carbon
V. Migrations of Silicon from Carbon to Oxygen
VI. Cyclopropane Openings and Closings
VII. Electrophilic Displacements with Allylic Rearrangement
References
Chapter 5 Polar 1, 2-Additions and Eliminations
I. Introduction
II. Carbon-Metal Hyperconjugation
III. Oxymercuration and Oxythallation
IV. Group IV Halide and Related Eliminations
V. Boron Halide Eliminations
VI. Hydroboration
VII. Hydralumination
VIII. Metal Alkyl Additions to Double Bonds
References
Chapter 6 Carbene Transfer Agents, Carbenes, and Related Topics
I. Introduction
II. Methylene Transfer Reagents
III. Dihalocarbenes
IV. Silenes and Fluoroborene
References
Chapter 7 Free-Radical and Photochemical Reactions
I. Introduction
II. Principles of Radical Chemistry
III. Replacements of Metal Atoms
IV. Lithium and Sodium Compounds and CIDNP
V. Silyl and Stannyl Radicals
VI. Neighboring Metal Atoms in Carbon Radicals
VII. Photochemistry
References
Chapter 8 Free Metals and Metal Anions
I. Introduction
II. Mercury Atoms and Mercury Surfaces
III. Thallium and Lead Compounds
IV. Formation of Grignard and Lithium Reagents
V. Organocopper Chemistry
VI. Group IV Anions
VII Notes on Some Topics Not Covered
VIII. Prognosis for Future Research
References
Author Index
Subject Index