Organometallic Chem [Splst Period'l Rpt Vol 06]

514 Pages·1978·41.223 MB·English

by  E. Abel, et al.,

A Specialist Periodical Report
Organometallic
C h em i s t ry
Volume 6
A Review of the Literature Published during 'I976
Senior Reporters
E. W. Abel, Department of Chemistry, University of Exeter
F. G. A. Stone, Department of Inorganic Chemistry, University of Brisfol
Reporters
D. A. Armitage, Queen Elizabeth College, University of London
B. L. Booth, University of Manchester Institute of Science and Technology
D. J. Cardin, Trinity College, Dublin
N. G. Connelly, University of Bristol
D. A. Edwards, University of Bath
J. A. S. Howell, University of Keele
J. P. Maher, University of Bristol
J. D. Odom, University of South Carolina, U.S.A.
T. Onak, California State University, Los Angeles, California, U.S.A.
A. D. Redhouse, University of Salford
S. D. Robinson, King's College, University of London
J .. .I Wardefl, University of Aberdeen
W. E. Watts, New University of Ulster, Northern Ireland
C. White, University of Shefield
The Chemical Society
Burlington House, London WIV OBN
ISBN :0 85186 551 8
ISS N :0 301 -0074
Library of Congress Catalog Card No. 72-83459
Copyright 0 1978
The Chemical Society
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means - graphic, electronic,
including photocopying, recording, taping or
-
information storage and retrieval systems without
written permission from The Chemical Society
Printed in Great Britain by
Adlard & Son Ltd.
Bartholomew Press, Dorking
Foreword
This Volume of the Specialist Periodical Reports ‘Organometallic Chemistry’
reviews the literature for the calendar year 1976, the twenty-fifth anniversary of the
recognition of the molecular structure of ferrocene. In the quarter of a century that
has now elapsed, the study of organometallic compounds has developed into a
distinct branch of chemistry, exerting strong influences on the classical inorganic,
physical, and organic divisions of the science.
The discovery of novel compounds formed by main-group and transition metals
with organic molecules continues undiminished. With the organoderivatives of the
transition metals, however, there is an increasing emphasis on the role the com-
pounds can play in organic syntheses and catalysis.
The format of this book follows that of previous Volumes in the series. In order to
keep the Volume to a manageable size several of our Reporters have again placed at
the end of their chapters bibliographies of papers not reviewed in the cursive text.
May 1977 E. W. Abel
F. G. A. Stone

Contents
Chapter 1 Group I: The Alkali and Coinage Metats 1
By J. L. Wardell
1 -Metals 1
Hydrocarbon Radical-anion and Dianion Alkali Metal
Compounds
Bimetallic Complexes
General Formation
Halogen-Metal Exchange
Metallation
Cyclopentadienyl and Fluorenyl Compounds
Alkenyl-, Vinyl-, and Alkynyl-alkali-metal Compounds
Alkyl- and Aryl-alkali Metal Compounds
2 Copper, Silver, and Gold 10
a-Bonded Complexes 10
Alkene and Alkyne Complexes 10
Carbonyl Complexes 11
Other a-bonded Complexes 11
+Bonded Compounds 12
Copper and Silver Compounds 12
cuprates 13
Gold 13
3 Appendix 16
Al kali-meta 1 Compounds 16
Alkali-metal Reactions 17
Organo-copper and -cuprate Compounds 18
Reactions 18
Chapter 2 Group It: The Alkaline Earths and Zinc and its
Congeners 19
By J. L. Wardell
1 Beryllium 19
2 Magnesium 20
Formation 20
vi Contents
Alkyl- and Aryl-magnesium Compounds 21
Rearrangements 21
Alkenyl-, Vinyl-, and Allyl-Grignard Reagents 22
Reactions with Carbonyl Compounds 24
Metal Catalysed Reactions 25
3 Calcium, Strontium, and Barium 26
4 Cadmium and Zinc 26
5 Mercury 28
Mercuration 28
Other Preparations 29
Mercuration of Alkenes 30
Properties 32
Anion Exchange and Complex Formation 32
Other Reactions 33
6 Bibliography 34
Chapter 3 Group 111: Boron 37
By J. D. Odom
1 Awards, Books, Reviews, and Dissertations 37
2 Tbree-co-ordinate Boron Compounds 38
Preparation 38
Reactions 40
Hydroboration 40
Other Reactions 42
3 Four-co-ordinate Boron Compounds 47
4 Boron-Nitrogen Compounds 50
5 Boron-containing Heterocyclic Compound3 51
6 Boron-containing Metal and Metalloid Compounds 55
7 Boron in Biological Molecules 57
8 Theoretical Studies 58
9 Catalysts, Patents, and Polymers 59
10 Physical Studies of Organoboranes 60
11 Bibliography 62
Contents vii
Chapter 4 The Carbaboranes, including their Metal Complexes 65
By T. Onak
1 Introduction and Reviews 65
2 Carbaborane Syntheses, Interconversions, and Reactions 65
3 a-Bonded Derivatives 66
4 Cage Metallocarbaboranes 68
5 Physical and Theoretical Studies 73
6 Bibliography 76
Chapter 5 Group 111: Aluminium, Gallium, Indium, and Thallium 78
By J. P. Maher
1 Introduction 78
2 Aluminium 78
Preparations, Reactions, and Complexes 78
Structures, Bonding, and Exchange Reactions 83
Organic Preparative Reactions 85
Transition Metal-Alane Complexes 91
3 GalliumandIndium 92
4 Thallium 94
Preparations and Complexes 94
Reactions 94
5 Bibliography 98
Chapter 6 Group IV: The Silicon Group 102
By D, A, Armitage
1 Introduction 102
2 The Carbon-Metal Bond 103
3 Catenation 129
4 Hydrides of Silicon, Germanium, and Tin 132
viii Contents
5 Radicals R@* and their Metal Derivatives 136
6 Nitrogen Derivatives 139
7 Phosphine, &sine, and Stibine Derivatives 145
8 Oxygen Derivatives 147
9 Sulphur and Selenium Derivatives 152
10 Halogen Derivatives 154
11 Bibliography 155
Chapter 7 Arsenic, Antimony, and Bismuth 162
By J. L. Wardell
1 Bivalent Species 162
2 Tervalent Species 162
Ylides 164
Arsonium Salts 165
3 Quinquevalent Species 165
4 Bibliography 167
Chapter 8 Metal Carbonyls 169
By E. W. Abel and F. G. A. Stone
1 Introduction 169
2 1.r. Spectroscopy and Matrix-isolation Studies 171
3 13C N.m.r. Studies and CO Ligand Site Exchange in Polynuclear
structures 173
4 Electron Spectra 173
5 Molecular Structure Determination by X-Ray Crystallography 174
6 Chemical ReactionS and New Compounds 176