Organometallic Chemistry of the Transition Elements

767 Pages·1990·62.512 MB·English

by  Florian P. Pruchnik, Stan A. Duraj (auth.)

Organometallic
0/
Chemistry the
Transition Elements
MODERN INORGANIC CHEMISTRY
Series Editor: John P. Fackler, Jr.
Texas A&M University
CARBON-FUNCTlONAL ORGANOSILICON COMPOUNDS
Edited by Vac1av Chvalovsky and Jon M. Bellama
GAS PHASE INORGANIC CHEMISTRY
Edited by David H. Russell
HOMOGENEOUS CAT ALYSIS
WITH METAL PHOSPHINE COMPLEXES
Edited by Louis H. Pignolet
THE JAHN-TELLER EFFECT AND
VIBRONIC INTERACTIONS IN MODERN CHEMISTRY
I. B. Bersuker
METAL INTERACTIONS WITH BORON CLUSTERS
Edited by Russell N. Grimes
MÖSSBAUER SPECTROSCOPY
APPLIED TO INORGANIC CHEMISTRY
Volumes 1 and 2 • Edited by Gary J. Long
Volume 3 • Edited by Gary J. Long and Fernande Grandjean
ORGANOMETALLIC CHEMISTRY OF THE
TRANSITION ELEMENTS
Florian P. Pruchnik
Translated from Polish by Stan A. Duraj
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Organometallic
Chmistry of the

Transition Elements
Florian P. Pruchnik
Universily 01 Wroclaw
Wroclaw, Poland
Translated from Polish by
Stan A. Dura}
Cleveland Stale Universily
Cleveland, Ohio
Springer Science+Business Media, LLC
Library of Congress Cataloging in Publication Data
Pruchnik, Florian P.
Organometallic chemistry of the transition elements / Florian P. Pruchnik: trans
lated from Polish by Stan A. Duraj.
p. cm. -(Modern inorganic chemistry.)
lncludes bibliographical references.
ISBN 978-1-4899-2078-2 ISBN 978-1-4899-2076-8 (eBook)
DOI 10.1007/978-1-4899-2076-8
I. Organometallic chemistry. 2. Transition metal compounds. I. Title. H. Series.
QD4.11. -P78 1990 89-71115
547'.056-dc20 CIP
© 1990 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1990.
Softcover reprint of the hardcover 1s t edition 1990
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Preface
Organometallic chemistry belongs to the most rapidly developing area of chemistry
today. This is due to the fact that research dealing with the structure of compounds
and chemical bonding has been greatly intensified in recent years. Additionally,
organometallic compounds have been widely utilized in catalysis, organic synthesis,
electronics, etc.
This book is based on my lectures concerning basic organometallic chemistry for
fourth and fifth year chemistry students and on my lectures concerning advanced
organometallic chemistry and homogeneous catalysis for Ph.D. graduate students.
Many recent developments in the area of organometallic chemistry as weIl as
homogeneous catalysis are presented. Essential research results dealing with a given
class of organometallic compounds are discussed briefly. Results of physicochemical
research methods of various organometallic compounds as weIl as their synthesis,
properties, structures, reactivities, and applications are discussed more thoroughly.
The selection of tabulated data is arbitrary because, often, it has been impossible to
avoid omissions. Nevertheless, these data can be very helpful in understanding properties
of organometaIlic compounds and their reactivities.
All physical data are given in SI units; the interatomic distances are given in pm
units in figures and tables.
I am indebted to Professor S. A. Duraj for translating and editing this book. His
remarks, discussions, and suggestions are greatly appreciated. I also express gratitude to
Virginia E. Duraj for editing and proofreading.
I sincerely thank Professor A. Wojcicki for his comments, discussions, and editorial
help. I also extend my thanks to Professors J. P. Fackler, Jr., F. A. Cotton, and
R. A. Walton for their suggestions and remarks.
My special thanks go to the chemistry faculty of Cleveland State University, espe
ciaIly to Professors A. H. Andrist and R. L. R. Towns for their support throughout the
translation of the book. I also sincerely thank RicheIle P. Emery for her exceIlent word
processing skills in connection with the preparation of the English manuscript.
The first Polish edition of this book appeared in 1984, and the second, expanded
edition is now in press.
v
vi Preface
I should also like to acknowledge the comments and discussions of Professors
S. Pasynkiewicz, A. Ratajczak, and W. Wojciechowski during the preparation of the
Polish editions of this book.
Finally, I sincerely thank my wife, Halina, for typewriting, proofreading, and for all
her help during the writing and preparation of the book.
F. Pruchnik
Contents
Chapter I. Introduction to Organometallic Chemistry
1. Number of Va!ence E!ectrons. Characteristics of Ligands. . . . . . . . . . . . . . . . .. . 1
2. The Main Group E!ements .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. The Transition Meta!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4. E!ementary Reactions of Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . 15
5. Nomenc1ature of Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References ............................................................. 20
Chapter 2. Metal Carbonyls
1. Preparation of Meta! Carbony!s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2. Bonding in Meta! Carbony!s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3. IR Spectra of Meta! Carbony!s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4. E!ectronic Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5. 13C NMR Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6. Photoe!ectron Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7. Mass Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
8. Properties of Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
a. Group 3 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
b. Group 4 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
c. Group 5 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
d. Group 6 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
e. Group 7 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
f. Group 8 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
g. Group 9 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Cluster Compounds of Co, Rh, and Ir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
h. Group 10 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Meta! Carbony! Halides of Group 10 Meta!s. . . . . . . . . . . . . . . . . . . . . . . . . . . 94
i. Group 11 Meta! Carbony!s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
9. Meta! Carbony! Hydrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
a. Bonding ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
b. Methods of Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
c. Preparation of Hydrido Comp!exes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 104
vii
viii Contents
d. Acidic Properties of Metal Carbonyl Hydrides. . . . . . . . . . . . . . . . . . . . . . . .. 107
e. Ligand Field Strength and trans Effect of the Hydrido Ligand .......... " 107
f. Structures of Hydrido Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 107
g. Properties of Metal Carbonyl Hydrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108
10. Metal Carbonyls Containing Bridging CO Groups Bonded Through C and 0 110
11. Thiocarbonyl and Selenocarbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . .. 112
a. Structure, Bonding, and Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 112
b. Preparation of Thiocarbonyl and Selenocarbonyl Complexes. . . . . . . . . . . .. 115
c. Reactions of Thiocarbonyl Complexes ........................ , . . . . . .. 116
12. Applications of Metal Carbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 119
13. Applications of Organometallic Compounds for Preparation of Metals,
Oxides, Carbides, and Nitrides, and for Deposition of Metal Layers and Their
Compounds ........................................................ 119
14. Metal Carbonyl Complexes Possessing Column Structures . . . . . . . . . . . . . . . .. 121
References ............................................................. 122
Chapter 3. Metal-Metal Bonds and Clusters
1. Bonding and Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 129
a. Theory of Ske1etal Electron Pairs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 133
b. The Isolobal Analogy of Fragments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 141
c. Topological Calculations of CVMO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 147
d. Reactions between Clusters ........................................ , 149
e. Molecular Orbital Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 150
2. Clusters as Models of Metallic Lattices of Catalysts . . . . . . . . . . . . . . . . . . . . . .. 155
3. Interstitial (Encapsulated) Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 157
4. "Electron Poor" Transition Metal Clusters. . . . . . . .. . . . ... . . .. . . .. . .. . . ... 160
5. NMR Spectra of Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 163
6. IR Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 165
7. The M - M Bond Energy in Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166
8. Synthesis of Metal Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166
9. Properties of Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 169
a. Group 4 ........................................................ " 169
b. Group 5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 170
c. Group 6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 170
d. Group 7.......................................................... 171
e. Group 8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 172
f. Group 9 ........................................................ " 174
g. Group 10. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 175
h. Group 11. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 177
10. Reactions of Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 179
a. Reactions Leading to Structural Changes in Clusters.. . .. . . .. . . ... . . . ... 180
b. Migration of Ligands Within Clusters .............................. " 183
c. Acid-Base Reactions ............................................. " 187
d. Ligand Substitution .............................................. " 190
e. Oxidative Addition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 190
References ............................................................. 193
Contents ix
Chapter 4. Compounds Containing le Carbon-Donor Ligands
1. Bonding in Compounds with Metal-Carbon Bonds. . . . . . . . . . . . . . . . . . . . .. 200
(J
2. Stability of Compounds Containing 1e Ligands . . . . . . . . . . . . . . . . . . . . . . . . . .. 201
3. Structure of Compounds Containing Metal-Carbon Bonds. . . . . . . . . . . . . .. 208
(J
4. IR and Raman Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 212
5. NMR Spectra . . . . .. . . . .. . . .. . . .. . . . .. . . . . . . . . . .. . . . .. . . . .. . . . . . . . . .. 213
6. ESR Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 215
7. Photoelectron Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 215
8. Magnetic Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217
9. Electronic Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 218
10. Preparation of Complexes Containing Bonded Carbon Ligands . . . . . . . . . .. 219
(J
a. Reactions of Transition Metal Compounds with Alkylating or Arylating
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 219
b. Reactions Involving Oxidative Addition of Organic Halides. . . . . . . . . . . . .. 220
c. Migration (Insertion) Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 222
d. Reactions of Anionic Complexes with Organic Halides. . . . . . . . . . . . . . . . .. 224
e. Elimination of Neutral Group Connecting Carbon with Metal
(Deinsertion) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 224
f. Preparation of Acetylide Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 225
g. Photochemical Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 225
h. Electrochemical Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 226
11. Properties of Complexes Containing Metal-Carbon Bonds .............. , 227
(J
a. Complexes of Group 3 Metals ...................................... , 227
b. Complexes of Group 4 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 229
c. Complexes of Group 5 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 232
d. Complexes of Group 6 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 232
e. Complexes of Group 7 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 234
f. Complexes of Group 8 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 238
g. Complexes of Group 9 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 242
h. Complexes of Group 10 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 244
i. Complexes of Group 11 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 249
12. Reactions of Complexes Containing Metal-Carbon Bonds. . . . . . . . . . . . . . .. 253
(J
a. The Breaking of the Metal-Carbon Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
b. Migration (Insertion) Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 255
c. Oxidative Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 260
d. The Rearrangement of Complexes Containing Metal-Carbon Bonds 261
(J-n; (J
13. Activation of Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 262
References ............................................................. 269
Chapter 5. Carbene and Carbyne Complexes
1. Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277
2. Structures of Carbene and Carbyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . . .. 281
3. IR Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 285
4. NMR Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 285
5. Photoelectron Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 287
6. Electronic Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 290
7. ESR and Magnetic Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 291