INORGANIC SYNTHESES Volume XIX Board of Directors W. CONARD FERNELIUS Kent Srate University WILLIAM L. JOLLY University of California HENRY F. HOLTZCLAW University ofNebraska JAY H. WORRELL University of South Florida FRED BASOLO Northwestern University ALAN G. MACDIARMID University ofPennsylvania BODIE E. DOUGLAS University of P irtsburgh Future Volumes XX DaryleH.Busch XXI John P. Fackler, Jr. XXII Smith L. Holt International Associates E. 0. FISCHER Technische Universitut (Munich) JACK LEWIS Cambridge University LAMBERTO MALATESTA University of Mifan F. G. A. STONE Brisrof University GEOFFREY WILKINSON Imperial College ofScience and Technology (London) AKIO YAMMOTO Tokyo lnstirute of Technology (Yokahama) Editor-in Chief DUWARD F. SHRIVER Department of Chemistry Northwestern University Evanston,.................... Illinois 60201 ..~................ INORGANIC SYNTHESES Volume XIX A Wiley-Interscience Publication JOHN WILEY & SONS New York Chichester Brisbane Toronto Published by John Wiley & Sons, Inc. Copyright @ 1979 Inorganic Syntheses, Inc All rights reserved. Published simultaneously in Canada. Repmduction or translation of any part of this work beyond that permitted by Sections 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 Cotalog Number: 39-23OI5 ISBN 0471-04542-X Printed in the United States of America I0987654321 PREFACE The wide range of synthetic techniques and compounds described here reflects the diversity of current inorganic chemistry. For example, the recent enthusiasm among inorganic chemists and solid-state physicists for studying anisotropic electronic conductors and fast-ion conductors is represented by a collection of syntheses for linear-chain conductors, layered tantalum sulfide intercalation compounds, and derivatives of the ionic conductor 0-alumina. A chapter on Werner-type complexes includes the first reliable synthesis of hydrido(tripheny1- phosphine)copper(I), as well as a variety of other useful compounds. The widespread interest in organometallic compounds prompted the inclusion of a large chapter containing subsections devoted to thiocarbonyl and carbene complexes and to improved syntheses for more familiar compounds, such as arenetricarbonylchromium complexes and pentacarbonylmanganese halides. Improved syntheses for important main group compounds, such as hexaborane and dimethylzinc, are given in the final chapter. In a significant departure from previous volumes, one chapter is devoted to syntheses based on a single technique, the codeposition of metal atoms with reactive substrates. Metal atom syntheses are of recent origin, and the techniques are not familiar to many chemists; therefore the decision was made to provide a detailed practical introduction to the method and to locate all of the metal atom syntheses in one chapter, irrespective of compound type. To ensure reliability, the procedures in Inorganic Syntheses are checked in a laboratory that is illdependent from that of the submitter, and the manuscripts are examined for clarity and completeness by the editor, with the help of the Editorial Board. I greatly appreciate the efforts of the submitters, checkers, and Editorial Board members who were willing to undertake these tasks. Recent editors who helped me in many ways during the preparation of ths book are Fred Basolo, Bodie Douglas, and George Parshall. I also appreciate suggestions made by Steven Ittel. Considerable help in the editing was provided by John Bailar, Conrad Fernelius, Smith Holt, Dennis Lehman, Warren Powell, Therald Moeller, and Thomas Sloan. I thank my secretary Madeleine Ziebka, who monitored the progress of manuscripts and efficiently handled many other chores. I have personally benefited from earlier volumes of Inorganic Synrheses, which stimulated my interest in synthetic inorganic chemistry when I was an under- V vi Preface graduate and later provided reliable syntheses for compounds that I needed in research. I hope that this new volume is equally useful to others. Duward F. Shriver Evanston, Illinois July 19 78 NOTICE TO CONTRIBUTORS 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 outstand- ing 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. An ideal synthesis is one that presents a new or revised experi- mental procedure applicable to a variety of related compounds, at least one of which is critically important in current research. However, syntheses of individual compounds that are of interest or importance are also acceptable. Syntheses of compounds that are available commercially at reasonable prices are not acceptable. The Editorial Board lists the following criteria of content for submitted manu- scripts. Style should conform with that of previous volumes of Inorganic Syntheses. The introductory section should include a concise and critical sum- mary 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 be reasonable for normal labor- atory 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 of 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 vii viii Notice to Contributors 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. Every synthesis must be satisfactorily reproduced in a laboratory other than the one from which it was submitted. Each manuscript should be submitted in duplicate to the Secretary of the Editorial Board, Professor Jay H. Worrell, Department of Chemistry, University of South Florida, Tampa, FL 33620. The manuscript should be typewritten in English. Nomenclature should be consistent and should follow the recommenda- tions presented in Nomenclature of Inorganic Chemistry, 2nd Ed., Butterworths & Co, London, 1970 and in Pure Appl. Chem., 28, No. 1 (1971). Abbreviations should conform to those used in publications of the American Chemical Society, particularly Inorganic Chemistry. TOXIC SUBSTANCES AND LABORATORY HAZARDS The obvious hazards associated with the preparations in this volume have been delineated in each experimental procedure but it is impossible to foresee and discuss all possible sources of danger. Therefore, the synthetic chemist should be familiar with general hazards associated with toxic, flammable, and explosive materials. Recently it has become apparent that many common laboratory chemicals have subtle biological effects that were not suspected previously. A list of 400 toxic substances is available in the Federal Register, Vol. 40, No. 23072, May 28, 1975, and an abbreviated version of this list is presented in Inorganic Syntheses, Vol. 18, p. xv, 1978. For a current assessment of the hazards of any particular chemical, see the most recent edition of Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment published by the American Conference of Governmental Industrial Hygienists. In light of the primitive state of our knowledge of the biological effects of chemicals, it is prudent that all the syntheses reported in this and other volumes of Inorganic Syntheses be conducted with rigorous care to avoid contact with all reactants, solvents, and products. Attention also must be given to the explosion and fire hazards presented by combustible organic vapors and combustible gases such as hydrogen and methane. These vapors are readily ignited by static electricity, electrical sparks from most laboratory appliances, open flames, and other highly exothermic reactions. Thus appreciable atmospheric concentrations of combustible vapors should be avoided. The drying of impure