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INORGANIC SYNTHESES Volume 32 INORGANIC SYNTHESES Volume 32 ....... Board of Directors BODIE E. DOUGLAS University of Pittsburgh HERBERT D. KAESZ University of California, Los Angeles DARY LE H. BUSCH University of Kansas JAY H. WORRELL University of South Florida RUSSELL N. GRIMES University of Virginia ROBERT J. ANGELIC1 lowa State University DONALD W. MURPHY AT&T Bell Laboratories LEONARD V. INTERRANTE Rensselaer Polytechnic Institute ALAN H. COWLEY University of Texas, Austin Future Volumes 33 DIMITRI COUCOUVANIS University of Michigan 34 JOHN R. SHAPLEY University of Illinois, Urbana 35 TOBIN MARKS Northwestern University 36 RICHARD J. LAGOW University of Texas, Austin International Associates MARTIN A. BENNETT Australian National University, Canberra FAUSTO CALDERAZZO University of Pisa E. 0. FISCHER Technical University, Munich M. L. H. GREEN Oxford University JACK LEWIS Cambridge University LAMBERTO MALATESTA University of Milan RENE POILBLANC University of Toulouse HERBERT W. ROESKY University of Gottingen F. G. A. STONE Baylor University H. VAHRENKAMP University of Freiburg AKIO YAMAMOTO Tokyo Institute of Technology Editor-in-Chief MARCETTA YORK DARENSBOURG ....................Texas A&M University .......... INORGANIC SYNTHESES Volume 32 A Wiley-Interscience Publication JOHN WILEY & SONS, INC. New York Chichester Weinheim Brisbane Singapore Toronto This book is printed on acid-fee paper. @ Copyright 0 1998 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (508) 750-8400, fax (508) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons,Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, e-mail: [email protected]. Library of Congress Catalog Number: 39-23015 ISBN 0-471-24921-1 Printed in the United States of America 10987654321 PREFACE The importance of continuing advances in ligand design for the role of coordination chemistry in research and practical applications can hardly be overstated. Thus a major focus of this volume of Inorganic Syntheses is on ligand synthesis. To assure that the associated organic synthesis does not overwhelm our inorganic tradition, in almost all cases examples of the synthesis of transition metal complexes using these ligands are also included. As indicated above, the term “continuing advances” signifies that future volumes could be similarly dedicated. Currently developing hot areas, such as the ligand-transition metal complex templating of the peptide bundle assembly, or ligands designed for stereoselective oxidation reactions, are not discussed herein. However, the mindful reader will undoubtedly find inspira- tion within this volume, from those ligands designed for other research purposes. Rather it is the bulk quantity, gram to multigram lots, of water- solubilizing phosphine ligands for organometallics already proven to be of importance to product and catalyst separation in industry that form the basis of Chapter 1. Included are phosphines made water soluble by sulfonation (i.e., ionic phosphines) and nonionic phosphines rendered water soluble by H-bonding interactions. During the past two decades, a remarkable synergism has developed in protein crystallography, enzymology, biophysical chemistry, and inorganic synthesis. The ligands and coordination complexes in Chapter 2 provide examples of attempts to model the function and form of the coordination environment of the active sites in metalloenzymes. The biomimetic ligand syntheses herein focus on models for the common metal-binding amino- acid residues histidine (imidazoles), cysteine (thiolates), and methionine (thioethers). Derivatives of the highly useful pyrazolylborates find form in syntheses producing neutral bi- and tridentate pyrazolyls, as well as several tripodal ligands. The requirement of isolated metal sites, which the protein catalyst so easily manages, has inspired the synthetic design of sterically bulky ligands, which has lead to abiological ligands and industrially impor- tant fundamental studies of small molecule activation. The initial entry of Chapter 3 proves that sophisticated ligands are not a requirement for useful coordination complexes. An alternative synthesis is offered for cisplatin, the widely used anticancer chemotherapeutic agent which contains the ultimate neutral ligand, ammonia. The coordination complexes of Chapter 3 traverse the periodic table and provide a number of vii ... VIII Preface labile ligand complexes which might be used as precursors for ligand ex- change with those of Chapters 2 and 3. Chapters 4 and 5 are contributed syntheses of cluster compounds and of hydrides. Although short, the hydride chapter presents pearls, epitomizing the spirit of Inorganic Syntheses for cleverly improved and useful syntheses. I was gratified to hear, during a workshop for new graduate students, the admonition to be skeptical of the literature, for it was only the collections of Inorganic Syntheses and Organic Syntheses that one could really trust to have been checked. Nevertheless, even with the rigorous reviewing and checking procedures of Inorganic Syntheses, there are occasional errors in interpreta- tion, and we acknowledge one such in Chapter 6. We are grateful to our readers for bringing this to our attention and to them as well as the original author for returning to the problem and sorting it out. Although many members of the editorial board of Inorganic Syntheses served as active reviewers of the submissions of this volume, two stand out for special recognition-Du Shriver and John Shapley. Du’s careful editing of all manuscripts that crossed his desk was the starting point for my own editing, and helped me considerably; John’s offer to check cluster syntheses went beyond the call of duty. In this regard, I must mention that the impact of Inorganic Syntheses on entire areas of development in inorganic chemistry depends on the enthusiasm or willingness (or lack thereof) of the checkers. To all contributors and checkers, I acknowledge my deepest gratitude. Finally, I must thank two undergraduates for keeping chaos at bay-Matthew Miller, a summer researcher from Grove City College, who responded to my call for help during the final assembly of the manuscript and Curtis Franke, a TAMU chemistry major/student worker, for his tremendous organizational skills while being the exemplar “Good Ag.” MARCETTAYORK DARENSBOURG College Station, Texas 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 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 experimental 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 reason- able prices are not acceptable. Corrections and improvements of syntheses already appearing in Inorganic Syntheses are suitable for inclusion. 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 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 ix x hbtice to Contributors and Checkers delineated clearly.
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