INORGANIC SYNTHESES Volume XXI .................... .*..................... Board of Directors HENRY F. HOLTZCLAW University of Nebrusku JAY H. WORRELL University of South Florida BODlE E. DOUGLAS University of Pittsbuurgh DUWARD F. SHRIVER Northwestern University DARYLE H. BUSCH Ohio Stute University Future Volumes XXII SMITH L. HOLT Oklahoma State University XXIII STANLEY KIRSCHNER WuyneStute University XXIV JEAN'NE M. SHREEVE University of Iduho XXV HERBERT D. KAESZ University of Culiforniu,Los Angeles International Associates E. 0. FISCHER Technische Universitat Munich JACK LEWIS Cambridge University LAMBERTO MALATESTA University of Milun F. G. A. STONE Universftyof Bristol GEOFFREY WILKINSON Imperiul College of Science und Technology London AKIO YAMAMOTO TokyoInstitute of Technology Yokohamu MARTIN A. BENNETT Austruliun Nutionul University R. POILBLANC Nation01 Center for Scientifc Research Toulouse H. W. ROESKY University Gottingen Editor-inChief JOHN P. FACKLER, JR. Department of Chemistry ....................Case Western Reserve....................... University INORGANIC SYNTHESES Volume XXI A Wiley-Interscience Publication JOHN WILEY & SONS New York Chichester Brisbane Toronto Singapore Published by John Wiley & Sons, Inc. Copyright 0 1982 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 -86520-6 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 PREFACE Inorganic Syntheses continues to fulfill a vital role for inorganic chemists and other users of inorganic and organometallic materials. Twenty volumes and 42 years have elapsed since Harold S. Booth edited the first volume in the series. While I did not have the opportunity to know Booth, his ghost occasionally returns to these halls at Case Western Reserve University to remind us of the great forward strides Inorganic Chemistry has made since World War 11. Who would have known then that chromous acetate (Inorganic Syntheses, Vol. I, 1939, p. 122) contains a metal-metal quadruple bond or that sulfur hexafluoride (Inorganic Syntheses, Vol. I, 1939, p. 121) would find such an important use as an electrical insulator? The objective of Inorganic Syntheses remains the same today as it was in 1939 when Roger Adams wrote: “The objective is to provide sufficient detail for each preparation so that a chemist of ordinary experience may duplicate the results on first trial.” As Editor-inChief of Volume MI, I have really learned what this means. Several submitted syntheses have, indeed, failed to meet this criterion, even though there was nothing suspect prior to actual checking. The community of chemists who check these syntheses perform an invaluable service. I am truly grateful for their help and extend to them my personal thanks. I encourage you to let editors of future volumes know if you are willing to check various types of syntheses. Your help will be appreciated and the service you render will be most beneficial to future generations of chemists. This volume has been divided (arbitrarily) into seven chapters. Chapter 1 con- tains some interesting syntheses of sulfur- and selenium-containing coordination compounds and clusters including the synthesis of the [Fe4S4(SR),] 2- species which R. H. Holm so elegantly identified as models for active sites in nonheme iron proteins. Compounds formed from SZ2- and SS2- are described. A conven- ient synthesis of CSe2 is reported. Several additional compounds relevant to biological sulfur chemistry are described. Dinuclear and polynuclear compounds continue to be synthesized in in- creasingly direct ways. Chapter 2 contains metal-metal bonded species such as those containing Pd-Pd or Mo=Mo and WEW bonds, mixed metal clusters, and compounds relevant to CO catalysis. Organometallic species again occupy a major section of this volume, Chapter 3. A chapter on coordination compounds, Chapter 4, also appears. It includes the first checked description of C02 mmplexes of Ir. The tris(2,2’-bipyridine) V vi Preface ruthenium(I1) chloride, well studied for its photochemical properties, is also reported. Chapter 5 is devoted to onedimensional tetracyanoplatinate com- plexes. The tetracNorooxotechretate(V) anion synthesis is described in Chapter 6 along with several other interesting stoichiometrically uncomplicated species. The use of technetium in medicine for imaging purposes has prompted renewed interest in this radioactive element. Several ligand syntheses are presented in Chapter 7, including the synthesis of pentamethylcyclopentodiene. A descrip- tion of the synthesis of the useful oneelectron reducing reagent VClz is also presented. In addition to thanking Fred Basolo and the Editorial Board who have generally encouraged me and given me help when needed, 1 wish to specifically thank Al Ginsberg, William Seidel, Steve Ittel, and Therold Moeller for the extra effort they have made to read or check manuscripts. Katherine Fackler helped with the initial organization of the volume and the indexing. Warren H. Powell and Thomas E. Sloan of the Chemical Abstracts Service again have kept the nomenclature up-todate and have improved the English found in many of the manuscripts. I appreciate the help of Du Shriver, J. Worrell, M. Dolores Abood, and Anthony M.Mazany in proofreading. Inorganic Syntheses first attracted my attention as an undergraduate at Vaparaiso University; but when I shared a laboratory as a graduate student with Professor Ralph C. Young at M.I.T., an early Associate Editor, I learned what Inorganic Syntheses was all about. My first personal copies of this work are due to his kindness. Previous volumes of Znorganic Syntheses are available. Volumes I-XVI can be ordered from Robert E. Krieger Publishing Co., Inc., 645 New York Avenue (or P.O. Box 542), Huntington, NY 11743; Volume XVII is available from McGraw- Hill, Inc.; and Volumes XVIII-XX can be obtained from John Wiley & Sons, Inc. JOHN P. FACKLER, JR. Cleveland, Ohio January I982 NOTICE TO CONTRIBUTORS AND CHECKERS The Inorganic Syntheses series is published to provide all users of inorganic sub- stances with detailed and foolproof procedures for the preparation of important and timely compounds. Thus the series is the concern fo the entire scientific community. The Editorial Board hopes that all chemists will share in the re- sponsibility of producing Inorganic Syntheses by offering their advice and as- sistance 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. An ideal synthesis is one that presents a new or revised experimen- tal 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 readily 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 Syn- theses. 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 de- tailed and unambiguous laboratory directions and be written so that it antici- pates 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 labo- ratory 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 vii viii Notice to Contributors and Checkers 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. 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.