PROGRESS IN INORGANIC CHEMISTRY Volume 11
Advisory Board THEODORE L. BROWX UNIVERSITY OF ILLINOIS, URBANA, ILLINOIS JAhlES P. COLLMAK STANFORD UNIVERSITY, STANFORD, CALIFORNIA F. ALBERT COTTON M.I.T., CAMBRIDGE, MASSACHUSETTS RILEY SCHAEFFER INDIANA UNIVERSITY, BLOOMINGTON, INDIANA GEOFFREY W ILKIXSON IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, LONDON, ENGLAND
PROGRESS IN INORGANIC CHEMISTRY EDITED BY STEPHEN J. LIPPARD DEPARTMENT OF CHEMISTRY COLUMBIA UNIVERSITY NEW YORK, NEW YORK VOLUME 11 INTERS CIEN CE PUBLISHERS 1970 a division of JOHN WILEY & SONS New York. London. Sydney. Toronto
The paper used in this book has a ph of 6.5 or higher. It has been used because the best information now available indicates that this will contribute to its longevity. Copyright 0 1970 by John Wiley & Sons, Inc. All Rights Reserved. No part of this book may be reproduced by any means, nor transmitted, nor translated into a machine language without the written permission of the publisher. Library of Congress Catalog Card Number 59-13035 SBN 471 54081 1 Printed in the United States of America
Preface to Volume 11 During the years that have elapsed since the inception of this series in 1959 there has been a proliferation of primary journal papers in all fields of chemistry, including inorganic. In an attempt to keep pace with this growth, several new review serials have appeared. In view of this information explosion, the original reasons (see Introduction to the Series by F. A. Cotton, reprinted in the present volume) for presenting a continuing collection of authoritative articles in which the progress in inorganic chemistry is reviewed seem all the more cogent. It is now clear, as it was a decade ago, that the problems of inorganic chemistry attract a diverse body of scientists throughout the world who sustain a vigorous research effort. This series aspires to provide them with a forum for the critical evaluation of results and for the comprehensive presentation of advanced knowledge in any given subject. The cross fertilization gained by printing articles on widely diversified topics in a single volume is highly valued. In order to facilitate these aims, no space or gross stylistic restrictions are imposed on the authors of individual contributions except that a table of contents is provided for the benefit of the casual reader. Because there are no space limitations, it is not always possible to predict the number of articles that will fit into a given volume. As a result there may be some delay in the publication of a manuscript, although every attempt will be made to avoid this problem. Reviews are usually solicited by the editor with the assistance of the Advisory Board. Manuscripts may be submitted for consideration, however. Criticisms and suggestions concerning the series are welcomed. In all cases the authors of the articles deserve credit for their excellence, and I am grateful for their cooperation. I also thank the members of the Advisory Board for their help. New York, New York March 10, 1969 S. J. LIPPARD
Introduction to the Series (reprinted from Volume 1) The remarkably broad and rapid development of inorganic chemistry since the end of World War IT is well recognized. If we chose to define inorganic chemistry as the study of all of the chemical and many related physical properties of inorganic substances, the extent of the field is very great indeed. It includes among its ramifications the organo derivatives of all of the elements, the study of mixed oxide systems, the quantum mechanical treatment of the spectral and magnetic properties of transition metal ions, the study of a wide variety of catalytically active solids, the preparation of a host of the less familiar elements and their compounds, as well as radically new types of compounds, along with the many classically recognized aspects of inorganic chemistry. The wide interest and the rapid growth and expansion of the field are attested by the great and persistent demand for inorganic chemists for both industrial and academic positions. The new Division of Inorganic Chemistry of the American Chemical Society, which received permanent status recently, symbolizes the general recognition of inorganic chemistry as a distinct and plenary branch of the science. Because of the breadth and diversity of the discipline, the problem of maintaining effective, fruitful communication among the different branches of inorganic chemistry has become highly important. It is my belief that a new forum for the exchange of views and for critical and authoritative review and evaluation of advances in the various branches of the discipline would be of great value. The annual series of volumes of which this is the first has been initiated with the hope that it will contribute to meeting the need for communication. It is intended that all articles be written by one of the leading researchers in the field. The treatment is intended to be such that the article should be comprehensible, but not necessarily readizy comprehensible, to a competent Ph.D. level research worker in some branch of inorganic chemistry, but not necessarily the one under discussion. However, it is my belief that the author's responsibility and privilege of giving a scholarly and accurate account of his subject should not be curtailed by any feeling of a need for oversimplification. If, for example, a subject is intrinsically complicated or mathematical, no useful purpose can be served by dealing with it as if it were not. Thus I have hoped to include articles which avoid both of the extremes, first, of dry and terse summarizing of the literature vii
... Vlll INTRODUCTION TO THE SERIES and, second, of superficiality suitable perhaps for light reading but not very helpful to the reader desiring accurate, thorough information. I have encouraged a degree of informality so that where responsible differences of opinion exist the expression of the author s own viewpoint, consistent with fairness and decorum, may be presented. Length and style will also be found to vary from one article to another, since I have assumed that the author is best qualified to determine the style, length, and general nature of the treatment appropriate to his subject. It is also my hope that these volumes will be regarded as, and become progressively more of, an international venture, which is in the true spirit of science. With this in mind, articles will be published in any of the three languages, English, German, and French, which research chemists are assumed to read. I should greatly welcome comments and suggestions with regard to any aspect of these volumes. In conclusion, it is my duty to emphasize that it is the authors of the articles who are responsible for their excellence and it is my pleasure to express my gratitude for their efforts. Cambridge, Massachusetts June 25, 1959 F. A. COTTON
Contents Vibrational Spectra and Metal-Metal Bonds BY THOMAS G. SPIRO, Department of Chemistry, Princeton University, Princeton, New Jersey.. 1 Transition Metal Complexes of Azulene and Related Ligands BY MELVYN R. CHURCHILL, Department of Chemistry, Harvard University, Cambridge, Massachusetts.. 53 Metal Tetrahydroborates BY B. D. JAMES AND M. G. H. WALLBRIDGE, Department of Chemistry, University of She#eld, She#eld, United Kingdom. 99 The Chemistry of the Dithioacid and 1,l-Dithiolate Complexes BY DIMITRI COUCOUVANIS, University of Iowa, Iowa City, Iowa. 233 Author Index.. 373 Subject Index.. 397 Cumulative Index, Volumes 1-11. * 403 ix