INORGANIC SYNTHESES Volume 27 .................... ................ Board of Directors JOHN P. FACKLER, JR. Texas A&M University BODlE E. DOUGLAS University of Pittsburgh SMITH L. HOLT, JR. Oklahoma State Uniuersity JAY H. WORRELL University of South Florida RUSSELL N. GRIMES University of Virginia ROBERT J. ANGELIC1 Iowa State University Future Volumes 28 ROBERT J. ANGELIC1 Iowa State University 29 RUSSELL N. GRIMES University of Virginia 30 LEONARD V. INTERRANTE Rensselaer Polytechnic Institute 31 ALLEN H. COWLEY University of Texas, Austin 32 MARCETTA Y. DARENSBOURG Texas A&M University International Associates MARTIN A. BENNETT Australian National University, Canberra FAUSTO CALDERAZZO University of Pisa E. 0. FISCHER Technical University. Munich JACK LEWIS Cambridge University LAMBERTO MALATESTA University of Milan RENE POILBLANC University of Toulouse HERBERT W. ROESKY University of Gottingen F. G. A. STONE University of Bristol GEOFFREY WILKINSON Imperial College of Science and Technology. London AKlO YAMAMOTO Tokyo Institute 01 Technology. Yokohama Editor-in-Chief ALVIN P. GINSBERG INORGANIC SYNTHESES Volume 27 A Wiley-Interscience Publication JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore A NOTE TO THE READER This book has been electronically reproduced from digital idormation stored at John Wiley h Sons, Inc. We are phased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings. Published by John Wiley & Sons, Inc. Copyright $? 1990 Inorganic Syntheses, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Catalog Number: 39-23015 ISBN 0-471-50976-0 PREFACE Inorganic Syntheses is 50 years old. The first volume, edited by Harold S. Booth, appeared in 1939 and contained 90 checked procedures. Booth, Professor of Chemistry at Western Reserve University, had seen a need for a series of volumes in which would appear detailed and tested procedures for the synthesis of inorganic compounds. His efforts to bring Inorganic Syntheses into being dated back to 1933 when he was joined in the venture by L. F. Audrieth, W. C. Fernelius, W. C. Johnson, and R. E. Kirk. To quote one of the cofounders: “It would be fair to say that the inauguration of Inorganic Syntheses was not a product of the times but more a reaction against the times. In the late 20’s and early 30’s of this century there were in this country only a few inorganic chemists and little research in the field” [W. C. Fernelius, “History of Inorganic Syntheses,” October 1983 (unpublished)]. Over the 50 years since Volume 1 appeared, research in inorganic chemistry has undergone an enormous expansion, and the Inorganic Syntheses series has grown to a total of 27 volumes containing more than 3000 checked procedures. Although it would be incorrect to claim that all of these procedures are foolproof [witness Inorg. Synth., 23, 199 (1985)], they do comprise the largest available collection of reliable preparations of inorganic compounds. The series has established itself as the reference of first resort for anyone with the need to synthesize an inorganic compound. The procedures in Inorganic Syntheses owe their reliability to the requirements that they be checked in a laboratory other than that of the submitters and that they be presented in detailed and unambiguous form. Both of these requirements frequently result in substantial modification of submitted manuscripts. The present volume contains over 200 syntheses, presented in 68 numbered sections grouped into nine chapters that correspond for the most part to Previous volumes of Inorganic Syntheses are available. Many of the volumes originally published by McGraw Hill. Inc. are available from R. E. Krieger Publishing Co., Inc.. P.O. BOX9542, Melbourne, FL 32901. Please write this publisher for a current list. Volumes out of print with John Wiley & Sons, Inc. are also available from Krieger Publishing. Recent back volumes can be obtained from John Wiley & Sons, Inc.. 605 Third Avenue, New York, NY 10158. Please write the publisher for a current list of available volumes. vii viii Prrfuce currently active areas of research. Although all of the chapters contain important and timely compounds, I would single out for special mention Chapter 3 on the early transition metal polyoxoanions. This chapter, organized and solicited by Walter G. Klemperer, addresses the synthesis of a class of compounds that are notably difficult to prepare in pure form. The successful preparation of many of these compounds requires close attention to the details of the procedure, and in several cases critical details taken for granted by the submitters were brought out by the checkers. An Inorganic Syntheses volume is the product of the efforts of many people. There are, of course, the submitters and checkers who produce the checked syntheses. In addition to these contributors, I would like to thank the following people for their efforts on behalf of Volume 27: Walter Klemperer for organizing Chapter 3 and providing an introduction to it; Andrea Wayda for organizing Chapter 4; Thomas E. Sloan and William Powell for advice on chemical nomenclature and for compiling the index; and the members of the Inorganic Syntheses Corporation who provided reviews of the submitted manuscripts, especially Bob Angelici, John Bailar, Dimitri Coucouvanis, and Therald Moeller. John Bailar and Therald Moeller also helped with checking the revised manuscripts. Finally, I thank Fred Basolo for efficiently resolving an awkward checking problem and Duward Shriver for his “Guide for Editors of Inorganic Syntheses”, which facilitated my task as Editor-in-Chief. ALVINP. GINSBERG Berkeley Heights, New Jersey February. 1990 NOTICE TO CONTRIBUTORS AND CHECKERS The Inorganic Syntheses series is published to provide all users of inorganic substances with detailed and foolproof procedures for the preparation of important and timely compounds. Thus the series is the concern of the entire scientific community. The Editorial Board hopes that all chemists will share in the responsibility of producing Inorganic Syntheses by offering their advice and assistance in both the formulation of and the laboratory evaluation of outstanding syntheses. Help of this kind will be invaluable in achieving excellence and pertinence to current scientific interests. There is no rigid definition of what constitutes a suitable synthesis. The major criterion by which syntheses are judged is the potential value to the scientific community. For example, starting materials or intermediates that are useful for synthetic chemistry are appropriate. The synthesis also should represent the best available procedure, and new or improved syntheses are particularly appropriate. Syntheses of compounds that are available commercially at reasonable prices are not acceptable. We do not encourage the submission of compounds that are unreasonably hazardous, and in this connection, authors are requested to avoid procedures involving perchlorate salts due to the high risk of explosion in combination with organic or organometallic substances. Authors are also requested to avoid the use of solvents known to be carcinogenic. The Editorial Board lists the following criteria of content for submitted manuscripts. Style should conform with that of previous volumes of Inorganic Syntheses. The introductory section should include a concise and critical summary of the available procedures for synthesis of the product in question. It should also include an estimate of the time required for the synthesis, an indication of the importance and utility of the product, and an admonition if any potential hazards are associated with the procedure. The Procedure should present detailed and unambiguous laboratory directions and be written so that it anticipates possible mistakes and misunderstandings on the part of the person who attempts to duplicate the procedure. Any unusual equipment or procedure should be clearly described. Line drawings should be included when they can be helpful. All safety measures should be stated clearly. Sources of unusual starting materials must be given, and, if possible, minimal standards of purity of reagents and solvents should be stated. The scale should ix x Notice to Coniributors and Checkers be reasonable for normal laboratory operation, and any problems involved in scaling the procedure either up or down should be discussed. The criteria for judging the purity of the final product should be delineated clearly. The section on Properties should supply and discuss those physical and chemical characteristics that are relevant to judging the purity of the product and to permitting its handling and use in an intelligent manner. Under References, all pertinent literature citations should be listed in order. A style sheet is available from the Secretary of the Editorial Board. The Editorial Board determines whether submitted syntheses meet the general specifications outlined above, and the Editor-in-Chief sends the manuscript to an independent laboratory where the procedure must be satisfactorily reproduced.