Principles of

Organometallic
Chemistry
 P. POWELL

Principles of
Organometallic
Chemistry
Second
edition

Springer-Sciencet Business Media, B. V.

 © 1988 P. Powell
Originally published by Chapman and Hall
Softcover reprint ofthe hardcover 2nd edition 1988

ISBN 978-94-010-7032-4 ISBN 978-94-009-1197-0 (eBook)

DOI 10.1007/978-94-009-1197-0

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British Library Cataloguing in Publication Data

Powell. P.
Principles of organometallic chemistry.
-2nd ed.
1. Organometallic compounds
!. Title
547'.05 QD4ll

Library of Congress Cataloging in Publication Data

Powell. P. (Paul). 1936-

Principles of organometallic chemistry 1 P. Powell.-2nd ed.
p.cm.
Rev. ed. of: Principles of organometallic chemistry 1 G.E. Coates
··· [et al.] .. 1968.
Includes bibliographies and index.

l. Organometallic chemistry. !. Principles of organometallic

chemistry. Il. Title.
QD41l.P64 1988 87-17193
547'.05-dc 19 CIP
 Contents

Foreword ix
Preface xi
Periodic table of the elements xiii

1. General survey 1
1.1 Introduction 1
1.2 Historical background 1
1. 3 Properties 2
1.4 Classification of organometallic compounds by bond type 2
1.5 The 'stability' of organometallic compounds 9
1.6 References 13

2. Methods of formation of metal-carbon bonds of the main

group elements 15
2.1 The reaction between a metal and an organic halogen
compound 15
2.2 Metal exchange: the reaction between a metal and an
organometallic compound of another metal 19
2.3 Reactions of organometallic compounds with metal halides 20
2.4 Addition of metal hydrides to alkenes and alkynes 22
2.5 Formation of metal-carbon bonds by other insertion
reactions 25
2.6 Reactions of diazo compounds 25
2. 7 Decarboxylation of heavy B-metal salts 27
2.8 References 28

3. Organometallic compounds of elements of the first three

periodic groups 29
3.1 Introduction 29
3. 2 Structures 31
3.3 Alkali-metal derivatives 39
3.4 Grignard reagents 50

V
Contents

3.5 Beryllium 54
3.6 Calcium, strontium and barium 56
3. 7 Zinc, cadmium and mercury 57
3.8 Organoboron compounds 65
3. 9 Organometallic compounds of Al, Ga, In and TI 80
3.10 Organocopper and -silver compounds 87
3.11 Complexes of main group elements with unsaturated
hydrocarbons 90
3.12 References 94
Problems 95

4. Organometallic compounds of elements of main Groups IV

and V 98
4.1 Introduction 98
4.2 Tetra-alkyls and -aryls of the elements of Group IV 99
4.3 Organohalides of the elements of Group IV 102
4.4 Silicones 109
4.5 Hydrolysis of organohalides of germanium, tin and lead 116
4.6 Catenated organic derivatives of the elements of Group IV 117
4.7 Divalent organic compounds of the elements of Group IV 121
4.8 pn-pn Bonding in compounds of Groups IV and V 124
4. 9 Organic derivatives of the elements of Group V 12 5
4.10 References 144
Problems 14 5

5. Some transition metal chemistry relevant to organometallic

chemistry 148
5.1 The 18-electron rule 148
5.2 Transition metal carbonyls 152
5.3 Some general reactions of transition metal complexes 173
5.4 References 186
Problems 18 7

6. Organometallic compounds of the transition elements.

Classification of ligands and theories of bonding 191
6.1 Classification of ligands 191
6.2 Molecular orbital theory 194
6.3 References 211
Problems 211

7. Organotransition metal chemistry. Alkyl and alkylidene

derivatives. Complexes of alkenes and alkynes 213
7.1 Alkyls and aryls 213
7.2 Alkylidene and alkylidyne (carbene and carbyne)
complexes 232

vi
 Contents

7.3 Complexes of alkenes 237

7.4 Complexes of alkynes 243
7. 5 References 248
Problems 249

8. Allyl and diene complexes of the transition elements 253

8.1 Allyl (-enyl) complexes 2 53
8.2 Diene complexes 263
8.3 References 272
Problems 2 72

9. Five electron ligands 278

9.1 Introduction 278
9.2 Bis(cyclopentadienyl) complexes- the metallocenes 279
9.3 Cyclopentadienylmetal carbonyls 292
9.4 Open-chain (acyclic) pentadienyl complexes 301
9.5 Cyclohexadienyltricarbonyliron salts 303
9.6 References 304
Problems 30 5

1 O. Complexes of arenes 311

10.1 Bis( arene )complexes 311
10.2 Arene(tricarbonyl)chromium complexes 316
10.3 Chemistry of some arene complexes of iron 320
10.4 Nucleophilic attack on organotransition metal complexes 321
10.5 tJ 6 -Cycloheptatriene and ry 7 -tropylium complexes 330
10.6 References 331
Problems 3 32

11. Cluster compounds 335

11.1 Introduction 335
11.2 Structure and bonding 335
11.3 Carboranes 340
11.4 Metallocarboranes and metalloboranes 344
11.5 Transition metal clusters 348
11.6 Clusters and catalysis 352
11.7 References 355
Problems 355

12. Mechanisms of industrial processes clarified by studies of

homogeneous catalysis by complexes of transition elements 357
12.1 Introduction 357
12.2 Resources 361
12.3 Catalysis of reactions of alkenes by transition metal
complexes 361

vii
Contents

12.4 Chemistry based on synthesis gas 383

12.5 Conclusion 395
12.6 References 395
Problems 397

13. Some complexes of the lanthanides and actinides 399

13.1 Introduction -lanthanides 399
13.2 Introduction-actinides 400
13.3 Cyclopentadienyls 400
13.4 Cyclooctatetraene complexes 402
13.5 References 403

Index 405

viii
 Foreword

The teaching of chemistry to undergraduate students presents course-content

problems which grow ever more difficult as huge amounts of new material are
added yearly to the overall body of the subject.
Some fifty years ago a student graduating with a good quality degree in
chemistry could be expected to ha ve a reasonable grasp of most areas, including a
fair number of recent developments. Since then, the explosion of knowledge has
made any such expectation quite unrealistic. Teachers of the subject continue,
however. to need texts to which they can refer students. The excellent but
mammoth compendia are clearly unsuitable for anything but reference.
Dr Powell's book provides a suitable anchor for students aiming at a useful
grasp of organometallic chemistry, especially that of the transition elements.
Applications of chemistry to industry often feature negligibly in undergraduate
courses; the chapter on industrial processes should help to remedy this
unfortunate situation.
The growth of organometallic chemistry over the past 40-50 years has been
immense. The present book can trace its ancestry to a 'slim volume' published in
19 5 5, almost the whole of the very short chapter on transition metals having
been added in the proof stage in 19 54. The third edition, written by three authors,
devoted an entire volume to transition metals. After the publication of this two
volume work, its authors decided that the book was no longer suitable for most
students, and that a text aimed at undergraduate students should be written. Dr
Powell was one of the four authors ofthe resulting book (19 68 ), and the present
volume stems from it.

G.E. Coates, M.L.H. Green and K. Wade

ix
 Preface

In the 20 years since 'Principles' first appeared the field of organometallic

chemistry has continued to expand very rapidly. During the 1950s and 1960s the
main theme was the preparation and structural characterization of new
compounds, especially those ofthe transition elements. The last two decades ha ve
seen the development of this theme and many unexpected materials such as
carbyne complexes and cluster compounds have been discovered. There is now
increasing emphasis on the application of organometallics of al! types in organic
synthesis, both in the laboratory and on an industrial scale.
These developments, although very exciting, present problems to anyone rash
enough to attempt to write an undergraduate text. Such a book should not be too
long and should present a balanced view ofthe field without becoming completely
indigestible through a mass of detail. The excellent reference work, 'Comprehen-
sive Organometallic Chemistry', published in 19 8 2, consists of 8 tomes and a large
index volume. Unfortunately, as Professor Coates has' remarked, "though the
content of science has grown so much, it is unlikely that the effective capacity of
students' brains has increased substantially over the past 15-20 years."
It has therefore been necessary to be very selective in the topics discussed.
Emphasis is laid on structures, bonding, methods of preparation and general
reactions of organometallic compounds. An elementary knowledge of thermody-
namics, bonding theory and the use of spectroscopic methods of structure
determination is assumed. The Periodic Groups provide a logica! framework for
treating the compounds of the typical elements. In the area of the transition
elements, however, the chemistry has been classified in terms of the electron
number of the principal ligand. The alternative approach, classification by
reaction type, can have the disadvantage that examples have to be drawn from
otherwise unrelated areas, which can prove confusing to the beginner.
The relevance of organometallic chemistry to industry has been indicated
throughout. Thanks are duc to severa! firms including Associated Octel. Bayer
AG, British Petroleum pic, Dow Corning, Esso and Thomas Swan & Co. Ltd. for
providing information in this connection. A chapter describes studies of the
mechanisms of homogeneously catalysed reactions. A few of these reactions are
used in industry. In other cases such mechanistic studies help to clarify how the
related heterogeneous systems, which are used in practice, may work.

xi
Preface

Some modern uses of organometallic compounds in specific organic synthesis

are indicated. Examples from natural product chemistry have mostly been
omitted, because at undergraduate level they may divert attention from the main
point.
Study problems ha ve been included at the end of chapters 3-12. A number of
these derive from the finals pa pers of various UK universities. In these cases the
name of the university is given at the end of the question, which bas been
reproduced by kind permission of that institution. A booklet containing answers
to these problems may be obtained by writing directly to the publishers.
Undergraduate students have little time to consult research papers or even
review articles. Consequently only a few references to textbooks and recent
reviews are given. Sources of further information are indicated, however, for
those who need them.
I am most grateful to Professor J.A. Connor, Professor T. Edmonds, Dr P.I.
Gardner, Dr M.L.H. Green, Dr P.G. Harrison and Dr D.M.P. Mingos for their
helpful suggestions during the preparation of the manuscript. I should like
especially to thank Professor G.E. Coates who read the complete text and made
many valuable comments. I would also like to thank the staff at Chapman and
Hali Ltd for their help and guidance during the production of the book.

P. Powell
Royal Holloway and Bedford New College,
University of London
]anuary 1988

xii
 Periodic table of
the elements

The periodic table overleafhas been included to give atomic weights for use in the
problems at the ends of chapters 3-12. These weights have been taken from the
IUPAC Inorganic Chemistry Division Commission on Atomic Weights and
Isotopic Abundances published in 1986 in Pure and Applied Chemistry, 58,
16 77-9 2. Brackets indicate that the weight of the commonest nuclide has been
given for a non-naturally occurring element.

xiii
 Periodic table of elements

Period Group Group Group Group Group Group Group Group

la Ilo !Ilo IVa Va Via VIla VIII
1 1 1 1 1
1 H
1 1
1 1
1 1
1s 1 1 1
1.01 1
1
1 1 1
1
1 1
3 4 1 1
1
2 1
Li Be 1 1 1
2s 2p 1 1 1
1 1
6.94 9.01 1 1
1
1 1
1
11 12 1 1
3 1 1
1
1

3s 3p Na Mg 1 1 1
1
1
1
1 1 1 1
22.99 24.31 1 1 1 1 1

19 20 21 22 23 24 25 26 27 28
4
K Ca Se Ti V Cr Mn Fe Co Ni
4s 3d4p
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69

37 38 39 40 41 42 43 44 45 46
5
Rb Sr y Zr Nb Mo Te Ru Rh Pd
5s4d5p
85.47 87.62 88.91 91.22 92.91 95.94 (99) 101.07 102.91 106.42

6 55 56 57* 72 73 74 75 76 77 78
6s (4fl Cs Ba La Hf Ta w Re Os lr Pt-
5d6p 183.85 186.21 190.20 192.22 195.08
132.91 137.32 138.91 178.49 180.95
87 88 89**
7
7s (5f) Fr Ro Ac
6d (223) (226) (227)

58 59 60 61 62 63 64 65
*Lanthanide
series Ce Pr Nd Pm Sm Eu Gd Tb
4f 140.12 140.91 144.24 (145) 150.36 151.97 157.25 158.93

90 91 92 93 94 95 96 97
**Achnide
series Th Pa u Np Pu Am Cm Bk
Sf 232 231 238 (237) (244) (243) (247) (247)

xiv
 Periodic table of elements

Group Group Group Group Group Group Group Group

lb llb lllb IVb Vb Vlb Vllb o
1 1 1 1 2
1
1
1
1
1
1
H He
1 1
1 1
1 1.01 4.. 00
1
1 7 8 9 10
1
5 6
1
1
8 c N o F Ne
1 10.81 12.01 14..01 16.00 19.00 20.18
1
1
1 13 14 15 16 17 18
1
1
Al Si p s CI Ar
1 26.98 28.09 30.97 32.07 35.45 39.95
1

29 30 31 32 33 34 35 36
Cu Zn Ga Ge As Se Br Kr
63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80

47 48 49 50 51 52 53 54
Ag Cd In Sn Sb Te 1 Xe
107.87 112.41 114.82 118.71 121.75 127.60 126.90 131.29

79 80 81 82 83 84 85 86
Au Hg TI Pb Bi Po M Rn
196.97 200.59 204.38 207.20 208.98 [-210) (-210) (-222)

66 67 68 69 70 71
Dy Ho Er Tm Yb Lu
162.50 164.93 167. 26 168.93 173.04 174.97

98 99 100 101 102 103

Cf Es Fm Md No Lr
(251) (252) [257) (258) (259) [260)

XV