Table Of ContentTOPICS IN INORGANIC
AND GENERAL CHEMISTRY
A COLLECTION OF MONOGRAPHS EDITED BY
R.J.H. CLARK
DEPARTMENT OF CHEMISTRY, UNIVERSITY COLLEGE LONDON, 20 GORDON STREET,
LONDON WC1H OAJ, ENGLAND
MONOGRAPH 19
OTHER TITLES IN THE COLLECTION:
1 The Chemistry of Beryllium, by D.A. Everest (out of print)
2 Inorganic Ion Exchanges, by C.B. Amphlett (out of print)
3 Introduction to the Atomic Nucleus, by J.G. Cuninghame (out of print)
4 The Chemistry of the Rare-Earth Elements, by N.E. Topp (out of print)
5 The Chemistry of Gallium, by I.A. Sheka, I.S. Chaus and T.T. Mityureva (out of
print)
6 The Chemistry of Technetium and Rhenium, by R.D. Peacock (out of print)
7 The Chemistry of Selenium, Tellurium and Polonium, by K.W. Bagnall (out of print)
8 Interactions in Electrolyte Solutions, by G.H. Nancollas (out of print)
9 Plasma Chemistry in Electrical Discharges, by F.K. McTaggart (out of print)
10 The Chemistry of Niobium and Tantalum, by F. Fairbrother (out of print)
11 The Chemistry of Titanium and Vanadium, by R.J.H. Clark
12 Active Carbon, by M. SmiSek and S. Öerny (out of print)
13 The Chemistry of Uranium (Including Its Applications in Nuclear Technology),
by E.H.P. Cordfunke (out of print)
14 The Chemistry of Thallium, by A.G. Lee (out of print)
15 The Actinide Elements, by K.W. Bagnall (out of print)
(Volumes 1—15 were edited by P.L. Robinson)
16 The Chemistry of Gold, by R.J. Puddephatt
17 Inorganic Chemistry in Liquid Ammonia, by D. Nicholls
18 Trace Chemistry of Aqueous Solutions, by P. BeneS and V. Majer
THE CHEMISTRY
OF RUTHENIUM
ELAINE A.SEDDON
S.E.R.C. Postdoctoral Fellow
School of Chemistry and Molecular Sciences
University of Sussex
Falmer
Brighton, BN1 9QJ
England
KENNETH R.SEDDON
Lecturer in Experimental Chemistry
School of Chemistry and Molecular Sciences
University of Sussex
Falmer
Brighton, BN1 9QJ
England
ELSEVIER
Amsterdam — Oxford — New York — Tokyo 1984
ELSEVIER SCIENCE PUBLISHERS B.V.
Molenwerf 1
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Distributors for the United States and Canada:
ELSEVIER SCIENCE PUBLISHING CO. INC.
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New York, N.Y. 10017
ISBN 0-444-42375-3 (Vol.19)
ISBN 0-444-41626-9 (Series)
© Elsevier Science Publishers B.V., 1984
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system or transmitted in any form or by any means, electronic, mechanical, photo-
copying, recording or otherwise, without the prior written permission of the publisher,
Elsevier Science Publishers B.V./Science & Technology Division, P.O. Box 330, 1000 AH
Amsterdam, The Netherlands.
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tained from the CCC about conditions under which photocopies of parts of this publica-
tion may be made in the USA. All other copyright questions, including photocopying
outside of the USA, should be referred to the publisher.
Printed in The Netherlands
TO LORD ALAN L.C. BULLOCK,
for his support and encouragement
vi
'Sometimes he spent hours together in the
great libraries of Paris, those cataccmbs
of departed authors, rummaging among their
hoards of dusty and obsolete works in quest
of food for his unhealthy appetite. He
was, in a manner, a literary ghoul, feeding
in the charnel-house of decayed literature."
Washington Irving (1783-1859)
The Adventure of the German Student
'For 'though it cannot hope to be useful or
informative on all matters, it does make
the reassuring claim that where it is
inaccurate, it is at least definitively
inaccurate. In cases of major discrepancy,
it is always reality that's got it wrong."
Douglas N. Adams (b. 1952)
The Hitch-Hiker's Guide to the Galaxy
vii
(i)
Rarer than platinum and very hard,
Underneath the Ukraine: nobody cared
Till Walt Whitman got to be twenty-five:
Hardy and Henry James were alive:
Elemental, subtle among alloys,
Not tarnishing in air: now it deploys
Isotopes like the branches of a tree
Under coordinative chemistry
More numerous than clouds over the sea.
(ii)
Mask, oxidize, fuse it in a green melt
Until it drops away an orange belt
In water, pure and stable to be felt.
No acid bites the natural metal,
Either palladium cements the wall
Hard as Hades or grey-white platinum,
Thor!s hammer would strike his own shoulder numb.
Uranus and Pluto, heaven and hell
Roared in their love-making: the child is well.
Peter Levi, 1979
Carl Ernst Claus (1796-1864)
ix
PREFACE
In the seventeenth century, Jean de la Bruyère wrote, "A man starts upon a
sudden, takes pen, ink and paper, and without ever having had a thought of it
before, resolves within himself he will write a Book; he has no talent at
.writing, but he wants fifty Guineas." More recently, George Orwell stated,
"Writing a book is a horrible, exhausting struggle, like a long bout of some
painful illness." We have some sympathy with these views, but are now, thank-
fully, convalescent. We venture to recall, however, that whilst suffering from
this painful illness, the agony was intensified by the cautious queries of "Is
it finished, yet?", which with the passage of time metamorphosed into the more
damning question, "Isn't it finished, yet?"
The preface traditionally outlines the scope, ordering and content of a book,
and is beloved of reviewers. To all reviewers, then, we apologise, but you will
have to read at least the first part of Chapter 1, as we judged this material
to be of sufficient importance to include it in the main text. Instead, we
intend to take this opportunity to express our sincere gratitude to all the
people who have helped us from the conception to the final production of this
monograph. Omnipresent has been our editor, Robin Clark, whose invaluable advice
has greatly reduced the number of errors in the text, and who taught us that to
react is intransitive. We also gratefully acknowledge the support of Elsevier
(but we still find camera-ready copy a necessary evil rather than a blessing
in disguise), and Alan Cocks, Tony Kallend and Tony Hart, of the Central
Electricity Generating Board. To Alan Cocks, who offered support, encouragement,
inspiration and friendship during my (K.R.S.) five years as a C.E.G.B. Fellow at
St. Catherine's College, I owe an especial acknowledgement, as it was out of our
many conversations that my interest in ruthenium was aroused. We would also like
to thank the C.E.G.B. for their financial support of this project, and the Master
and Governing Body of St. Catherine's College for the excellent facilities which
they provided to ease the birth pangs of the opening chapters. In this context,
we are particularly appreciative of the generous help given by Peter Levi (who
has written the only verse ever dedicated to ruthenium), Mike Shotton and
Richard Parrish (who respectively translated Russian and French manuscripts for
us). We would also like to thank Carla Cauletti for her help with Italian, Cathie
Rae and Buffy for their invaluable aid with the filing, Gillian for her consider-
ation and understanding, Dr. Shaw and all of his remarkably helpful and
cooperative staff at the Radcliffe Science Library in Oxford (especially Barbara,
χ
Ruth, Pat, Val and Theo) for their aid, and Professor J.B. Goodenough for his
continual support and encouragement, not to mention his permission to use the
facilities of the Inorganic Chemistry Laboratory.
No acknowledgements would be complete without mention of the huge debt we
both owe to our respective parents, without whose support and understanding
this book would not have been possible. Moreover, we wish to take this
opportunity to thank Mr. Holden, Mr. Howard and Mr. Brook (who shaped our
interest in Chemistry) and Dave Nicholls and Jenny Green, who were our guides
and mentors during our respective graduate studies. In particular, we wish to
thank Jenny for her understanding and forbearance, particularly during the last
stages of the completion of the manuscript, and Val, Sue, Ray, Ed, Russell, Pete,
Jan, Roger and a string of long-suffering Part II students who have endured (or
enjoyed?) our frequent absences from the laboratory. To Buffy, we are eternally
grateful for all the holidays she has given up to help us complete this
monograph. We also wish to thank John Holloway, Dave Rice, Kathleen C. Taylor,
Joe Earley, Mike Pilling, Peter Day and Tony Stephenson for their correspondence
and pre-publication data, Professor Goodenough and Peter Day for their helpful
comments upon certain parts of this manuscript, and Malcolm and Jenny Green for
their encouragement, invaluable aid (including access to their own unpublished
manuscript) and comments upon Chapter 2. Permission to publish the frontispiece,
the introductory quote from ' The Hitch-Hiker1 s Guide to the Galaxy1, the
introductory poem, and the extracts from "Nomenclature of Inorganic Chemistry"
in Chapter 2 from Johnson Matthey, Douglas Adams, Peter Levi and IUPAC,
respectively, is gratefully acknowledged, and we also thank all the chemists
who took the time and trouble to send us reprints of their papers.
Finally, we come to the people who have been of crucial importance to this
book appearing in its present form. To Vera Kastner, who typed the first part
of the draft manuscript so expertly, we owe a huge debt. Our thanks are also
due to Mark Atkinson for his help with the library work, to Heather Bunting for
her expert indexing and invaluable comments on the text, to Christine Palmer
for her excellent, accurate and clear artwork, and to Keith Waters for so
expertly producing the photographic prints, from Christine's drawings, which
have been used exclusively in the final preparation of the c.r.c. manuscript.
Without the help of Christine and Keith, and their respective skills which were
given with such willingness and friendliness, the presentation of this volume
would have been far below the excellent standard which their work has set.
However, undoubtedly the singly most important person in the production of this
book is Caron Crisp. Caron not only typed most of the draft manuscript,
but also typed the majority of the c.r.c. manuscript for this monograph. She is
responsible for the immaculate layout, the clarity and consistency of the text,
and the presentation of all the flow-diagrams, tables, schemes and equations.
xi
This task was performed in spite of our awful handwriting, inconsistent
presentation, poor spelling, and scripts which frequently resembled the work
of Kandinsky. So, to Caron goes the biggest and most heartfelt thank-you of
them all. THANK YOU.
Broadhill K.R. SEDDQN
August, 1983 E.A. SEDDQN
