Table Of ContentCOMPREHENSIVE COORDINATION CHEMISTRY
The Synthesis, Reactions, Properties & Applications of
Coordination Compounds
Editor-in-Chief: Sir Geoffrey Wilkinson, FRS
Executive Editors: Robert D. Gillard & Jon A. McCleverty
Pergamon
An imprint of Elsevier Science
COMPREHENSIVE
COQRDINATION CHEMISTRY
IN 7 VOLUMES
PERGAMON MAJOR REFERENCE WORKS
Comprehensive Inorganic Chemistry (1973)
Comprehensive Organic Chemistry (1 979)
Comprehensive Organometallic Chemistry (1 982)
Comprehensive Heterocyclic Chemistry (1 984)
International Encyclopedia of Education (1985)
Comprehensive Insect Physiology, Biochemistry & Pharmacology (1985)
Comprehensive Biotechnology (1985)
Physics in Medicine & Biology Encyclopedia (1986)
Encyclopedia of Materials Science & Engineering (I 986)
World Encyclopedia of Peace (1986)
Systems & Control Encyclopedia (1987)
Comprehensive Coordination Chemistry (1 987)
Comprehensive Polymer Science (1988)
Comprehensive Medicinal Chemistry (I 989)
COMPREHENSIVE
COORDINATION CHEMISTRY
The Synthesis, Reactions, Properties
& Applications of Coordination Compounds
Volume 2
Ligands
EDITOR-IN-CHIEF
SIR GEOFFREY WILKINSON,
FRS
Imperial College of Science & Technology, University of London, UK
EXECUTIVE EDITORS
ROBERT D. GILLARD JON A. McCLEVERTY
University CoUege, Cardif, UK University of Birmingham, UK
PERGAMON PRESS
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First edition 1987
Library o€ Congress Cataloging-in-PublicationD ata
Comprehensive coordination chemistry.
Includes bibliographies
Contents: v. 1. Theory and background - v. 2. Ligands - v. 3.
Main group and early transition elements - [etc.]
1. Coordination compounds.
I. Wdkinson, Geoffrey, Sir, 1921-
11. Gillard, Robert D.
111. McCleverty, Jon A.
QD474.C65 1987 541.2’242 86- I2319
British Library Cataloguing in Publication Data
Comprehensive coordination chemistry: the synthesis,
reactions. properties and applications of coordinabon
compounds.
1. Coordination compounds.
I. Wilkinson, Geoffrey, 1921-
11. Gdlard, Robert D.
111. McCleverty, Jon A.
541.2‘242 QD474
lSBN 0-08-035945-0(v o~.2 )
ISBN 0-08-026232-5 (set)
Printed in Great Britain by A. Wheaton & Co. Ltd., Exeter
1
Contents
Preface ix
Contributors to Volume 2 xi
Contents of All Volumes xv
11 Mercury as a Ligand 1
P. A. W. DEANU, niversity of Western Ontario, London, Ontario, Canada
Group IV Ligands
12.1 Cypimis and Fulminates 7
A. G. SHARPEU, niversity of Cambridge, UK
12.2 Silicon, Germanium, Tin and Lead 1s
P. G. HARRISONan d T. KIKABBAIU, niversity of Nottingham, UK
Nitrogen Ligands
13.1 Ammonia and Amines 23
D. A. HOUSE,U niversity of Canterbury, Christchurch, New Zealand
13.2 Heterocyclic Nitrogen-donor Ligands 73
J. REEDIJKLe, iden University, The Netherlands
13.3 Miscellaneous Nitrogen-containing Ligands 99
B. F. G. JOHNSON, University ojcumbridge, UK,B . L. HAYMORME,o nsanto Com-
pany, St Louis, MO, USA, and J. R. DILWORTUHn,i versity of Essex, Colchester, UK
13.4 Amido and Imido Metal Complexes 161
M. H. CHISHOLMIn,d iana University, Bloomington, IN, USA, and I. P. ROTHWELL,
Purdue University, West Lafayette, IN, USA
13.5 Sulfurdiimine, Triazenido, Azabutadiene and Triatomic Hetero Anion Ligands 189
K. VRIEZEan d G. v.4~K OTENU, niversity of Amsrerdam, The Netherlands
13.6 Polypyrazolylborates and Related Ligands 245
A. SHAVERM, cGiIl University, Montreal, Quebec. Canada
13.7 Nitriles 26 1
H. ENDRES,U niversity of Heidelberg, Federal Republic of Germany
13.8 Oximes, Guanidines and Related Species 269
R. C. MEHROTRAU,n iversity of Rajasthan, Jaipur, India
14 Phosphorus, Arsenic, Antimony and Bismuth Ligands See below
Oxygen Ligands
15.1 Water, Hydroxide and Oxide 295
J. BURGESSU, niversity oj Leicester, UK
15.2 Dioxygen, Superoxide and Peroxide 315
H. A. 0. HILL, University of Oxford, UK, and D. G. TEW,U niversity of California,
San Francisco, CA, USA
vi Con tents
15.3 Alkoxides and Aryloxides 33s
M. H. CHISHOLYIn. diana University, Bloomingzglon, IN, USA, and I. P. ROTHWELL,
Purdue University, West Lafayette, IN, USA
15.4 Diketones and Related Ligands 365
A. R. SIEDLE3,M Central Research Laboratories, St Paul, MN, USA
15.5 Oxy anions 413
B. J. HATHAWAUYn, iversitjJ College, Cork, Republic of Ireland
15.6 Carboxylates, Squarates and Related Species 435
C. OLDHAMU, niversit-v of Lancuster, UK
15.7 Hydroxy Acids 46 1
J. D. PEDROSDAE JESUS. University of Aveiro, Portugal
15.8 Sulfoxides, Amides, Amine Oxides and Related Ligands 487
P. L. GOGGINU, niversity of Bristol, UK
15.9 Hydroxamates, Cupferron and Related Ligands 505
R. C. MEHROTRAUn, iversity of Rajusthan, Jaipur, India
Surfur Ligands
116.1 Sulfides 515
A. MULLERa nd E. DIEMANNU,n iversity of Bielejeld, Federal Republic of Germany
16.2 Thioethers 55 1
A. MULLERa nd E. DIEMANKU,n iversity of Bielefeld, Federal Republic of Germany
16.3 Metallothio Anions 5 59
A. MULLERa nd E. DIEMANKU,n iversity of Bielefeld, Federal Republic of Germany
16.4 Dithiocarbamates and Related Ligands 579
J. A. CRASa nd J. WILLEMSEU,n iversity of Nijmegen, The Netherlands
16.5 Dithiolenes and Related Species 595
U. T. MUELLER-WESTERHaQndF FB . VANCEU, niversity of Connecticut, Storm, CT,
USA
16.6 Other Sulfur-containing Ligands 63 3
S. E. LIVINGSTONUEn,i versity of New South Wales, Kensington, NS W,A ustralia
17 Selenium and Tellurium Ligands 66 1
F. J. BERRYU, niversity of Birmingham, UK
18 Halogens as Ligands 675
A. J. EDWARDSU, niversity of Birmingham, UK
19 Hydrogen and Hydrides as Ligands 689
R. H. CRABTREEYa, le University, New Haven, CT, USA
Mixed Donor Atom Ligands
20.1 Schiff Bases as Acyclic Polydentate Ligands 715
M. CALLIGARaInSd L. RANDACCIOU,n iversita di Trieste, Italy
20.2 Amino Acids, Peptides and Proteins 739
S. H. LAURIEL, eicester Pojytechnic, UK
20.3 Complexones 777
G. ANDEREGGE,T H, Zurich, Switzerland
20.4 Bidentate Ligands 193
R. S. VAGGM, acquarie University, New South Wales, Australia
1
Cont ents vii
Multidentate Macrocyclic Ligands
21.1 Porphyrins, Hydroporphyrins, Azaporphyrins, Phthalocyanines, Corroles, Corrins 813
and Related Macrocycles
T. MASHIKaOn d D. DOLPHINU,n iversity of British Columbia, Vancouver, BC, Canada
21.2 Other Polyaza Macrocycles 899
N. F. CURTISY, ictoria University of Wellington, New Zealand
21.3 Macropolycyclic Ligands 9i5
K. 8.M ERTESU, niversity oj'Kansas, Lawrence, KS, USA, and J.-M. LEHN,U niversitk
Louis Pasteur, Strasbaurg, France
22 Naturally Occurring Ligands 9 59
S. H. LAURIEL, eicester Polytechnic, UK
14 Phosphorus, Arsenic, Antimony and Bismuth Ligands 989
C. A. MCAULIFFEU, niversity of Manchester Institute of Science and Technology, UK
Subject Index 1067
Formula Index 1105
Preface
Since the appearance of water on the Earth, aqua complex ions of metals must have existed. The
subsequent appearance of life depended on, and may even have resulted from, interaction of metal
ions with organic molecules. Attempts to use consciously and to understand the metal-binding
properties of what are now recognized as electron-donating molecules or anions (ligands) date from
the development of analytical procedures for metals by Berzelius and his contempories. Typically,
by 1897, Ostwald could point out, in his ‘ScientificF oundations of Analytical Chemistry’, the high
stability of cyanomercurate(I1) species and that ‘notwithstanding the extremely poisonous character
of its constituents, it exerts no appreciable poison effect’. By the late 19th century there were
numerous examples of the complexing of metal ions, and the synthesis of the great variety of metal
complexes that could be isolated and crystallized was being rapidly developed by chemists such as
S. M. Jsrgensen in Copenhagen. Attempts to understand the ‘residual affinity? of metal ions for
other molecules and anions culminated in the theories of Alfred Werner, although it is salutary to
remember that his views were by no means universaIIy accepted until the mid 1920s. The progress
in studies of metal complex chemistry was rapid, perhaps partly because of the utility and economic
importance of metal chemistry, but also because of the intrinsic interest of many of the compounds
and the intellectual challenge of the structural problems to be solved.
If we define a coordination compound as the product of association of a Bronsted base with a
Lewis acid, then there is an infinite variety of complexing systems. In this treatise we have made an
arbitrary distinction between coordination compounds and organometallic compounds that have
metal-carbon bonds. This division roughly corresponds to the distinction -w hich most but not all
chemists would acknowledge as a real one- between the cobalt(II1) ions [Co(NH,),]’+ and
[Co(q5-C5H,),]+A. ny species where the number of metal-carbon bonds is at least half thecoordina-
tion number of the metal is deemed to be ‘organometallic’a nd is outside the scope of our coverage;
such compounds have been treated in detail in the companion work, ‘Comprehensive Organo-
metallic Chemistry’. It is a measure of the arbitrariness and overlap between the two areas that
several chapters in the present work are by authors who also contributed to the organometallic
volumes.
We have attempted to give a contemporary overview of the whole field which we hope will provide
not only a convenient source of information but also ideas for further advances on the solid research
base that has come from so much dedicated effort in laboratories all over the world.
The first volume describes general aspects of the field from history, through nomenciature, to a
discussion of the current position of mechanistic and related studies. The binding of ligands
according to donor atoms is then considered (Volume 2) and the coordination chemistry of the
elements is treated (Volumes 3, 4 and 5) in the common order based on the Periodic Table. The
sequence of treatment of complexes of particular ligands for each metal follows the order given in
the discussion of parent ligands. Volume 6 considers the applications and importance of coordina-
tion chemistry in several areas (from industrial catalysis to photography, from geochemistry to
medicine). Volume 7 contains cumulative indexes which will render the mass of information in these
volumes even more accessible to users.
The chapters have been written by industrial and academic research workers from many
countries, all actively engaged in the relevant areas, and we are exceedingly grateful for the arduous
efforts that have made this treatise possible. They have our most sincere thanks and appreciation.
We wish to pay tribute to the memories of Professor Martin Nelson and Dr Tony Stephenson who
died after completion of their manuscripts, and we wish to convey our deepest sympathies to their
families. We are grateful to their collaborators for finalizing their contributions for publication.
Because of ill health and other factors beyond the editors’ control, the manuscripts for the
chapters on Phosphorus Ligands and Technetium were not available in time for publication.
However, it is anticipated that the material for these chapters will appear in the journal Polyhedron
in due course as Polyhedron Reports.
We should also like to acknowledge the way in which the staff at the publisher, particularly
coc 2-A’ ix
