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Inorganic-Synthesis28.Pdf REAGENTS FOR TRANSITION METAL COMPLEX AND ORGANOMETALLIC SYNTHESES INORGANIC SYNTHESES Volume 28 .................... .......................... Board of Directors JOHN P. FACKLER, JR. Texas A & M University BODIE E. DOUGLAS University of Pittsburgh DARYLE H. BUSCH University of Kansas JAY H. WORRELL University of South Florida HERBERT D. KAESZ University of Calijornia, Los Angeles ALVIN P. GINSBERG AT&T Bell Laboratories Future Volumes 29 RUSSELL N. GRIMES University of Virginia 30 LEONARD V. INTERRANTE Rensselaer Polytechnic Institute and DONALD MURPHY AT&T Bell Laboratories 31 ALAN H. COWLEY University of Texas 32 MARCETTA Y. DARENSBOURG Texas A & M University International Associates MARTIN A. BENNETT Australian National University, Canberra FAUSTO CALDERAZZO University of Piso E. 0. FISCHER Technical University, Munich JACK LEWIS Cadridge University LAMBERTO MALATESTA University of Milan RENE POILBLANC University of Toulouse HERBERT W. ROESKY University of Gottingen F. G. A. STONE University of Bristol AKIO YAMAMOTO Tokyo Institute of Technology, Yokohama Editor-in-Chief ROBERT J. ANGELIC1 Department of Chemistry lowa State University .--_.... ooooooooooooooooooooooooooooooooooooooaoaooaooo REAGENTS FOR TRANSITION METAL COMPLEX AND ORGANOMETALLIC SYNTHESES INORGANIC SYNTHESES Volume 28 A WILEY-INTERSCIENCE PUBLICATION John Wiley & Sons, Inc. NEW YORK / CHICHESTER / BRISBANE / TORONTO / SINGAPORE In recognition of the importance of preserving what has been written, it is a policy of John Wiley & Sons, Inc. to have books of enduring value published in the United States printed on acid-free paper, and we exert our best efforts to that end. Published by John Wiley & Sons, Inc Copyright (0 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: 3%23015 ISBN 0-47 1-52619-3 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 PREFACE This is a special volume of Inorganic Syntheses that focuses on complexes that are likely to be useful as starting materials for the preparations of new transition metal coordination and organometallic compounds. There are chapters on complexes with weakly coordinated and therefore easily dis- placed ligands, low-valent complexes that undergo oxidative-addition reac- tions, substituted metal carbonyl complexes, nucleophilic metal carbonyl anions, transition metal clusters, a variety of cyclopentadienyl complexes, lanthanide and actinide complexes, and a range of other useful ligands and complexes. Most of the syntheses are taken from previous volumes of Inorganic Syntheses; however, in each case the original author@), or in one case someone very familiar with the synthesis, was asked to correct errors, add safety notes, or make changes in the references. In several instances, .experi- mental procedures were modified; where these modifications were sub- stantive, the new procedures were repeated by checkers. There are nine totally new syntheses that I solicited, and these were checked in the usual manner. This project began in 1983 when Duward F. Shriver, who was President of Inorganic Syntheses, Inc. at the time, asked me to chair a committee with Russell N. Grimes and Herbert W. Roesky as members to explore the advisability of publishing a collective topical volume of Inorganic Syntheses on “basic starting materials.” The committee recommended that a volume on starting materials for the synthesis of transition metal complexes be pub- lished. I agreed to serve as Editor-in-Chief of the volume and solicited opinions of all members of Inorganic Syntheses for suggestions of syntheses that should be included. From these many very helpful comments, I compiled a list of preparations, most of which are in this volume. The compounds were Previous volumes of Inorganic Synthesesare available. Many of the volumes originally published by McGraw Hill, Inc. are available from R. E. Krieger Publishing Co., Inc., P.O. Box 9542, 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 Prefuce chosen with the thought in mind that this volume would be a primary source of synthetic procedures for those who have need to prepare transition metal complexes. The success of a volume like this depends upon a large number of people- those whose manuscripts are included, those who made suggestions, those who prepared new manuscripts, and especially those who verified the proced- ures by repeating them. Their cooperation made my task easier than it might have been. I am grateful to Thomas Sloan for compiling the indices. Also, many thanks to Carla Holbrook who provided cheerful, accurate, and efficient secretarial support of this project. ROBERTJ. ANGELICI Ames, Iowa September 1989 TOXIC SUBSTANCES AND LABORATORY HAZARDS Chemicals and chemistry are by their very nature hazardous. Chemical reactivity implies that reagents have the ability to combine. This process can be sufficiently vigorous as to cause flame, an explosion, or, often less immediately obvious, a toxic reaction. The obvious hazards in the syntheses reported in this volume are de- lineated, where appropriate, in the experimental procedure. It is impossible, however, to foresee every eventuality, such as a new biological effect of a common laboratory reagent. As a consequence, all chemicals used and all reactions described in this volume should be viewed as potentially hazardous. Care should be taken to avoid inhalation or other physical contact with all reagents and solvents used in procedures described in this volume. In addition, particular attention should be paid to avoiding sparks, open flames, or other potential sources that could set fire to combustible vapors or gases. A list of 400 toxic substances may be found in the Federal Register, Vol. 40, No. 23072, May 28, 1975. An abbreviated list may be obtained from Zn- organic Syntheses, Volume 18, p. xv, 1978. A current assessment of the hazards associated with a particular chemical is available in 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. The drying of impure ethers can produce a violent explosion. Further information about this hazard may be found in Inorganic Syntheses, Volume '12, p. 31 7. A hazard associated with the synthesis of tetramethyldiphosphine disulfide [Inorg. Synth., 15, 186 (1974)l is cited in inorganic Syntheses, Volume 23, p. 199. ix 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 com- mercially at reasonable prices are not acceptable. We do not encourage the submission of compounds that are unreasonably hazardous, and in this connection, less dangerous anions generally should be employed in place of perchlorate. The Editorial Board lists the following criteria of content for submitted manuscripts. Style should conform with that of previous volumes of Zn- organic 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 be reasonable for normal laboratory operation, and xi xii Notice to Contributors and Checkers any
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