4S Ch. Elschenbroich, A. Salzer Organometallics ~' A Concise Introduction |. Revised EditionChristoph Elschenbroich Albrecht Salzer Organometallics A Concise Introduction Second. Revised Edition >) VCH Weinheim - New York - Basel » Cambridge.the German cat gehenbroicl Salzer Organometalichemie, 3. Aufl, Srutigart, 1991: FI sjschenbroich rublisher of BG Teubnet. prof Dr Chnistoplt E Fachbereich Chem | ailpps Universitat Marbure Hans Meerwein-Str [p-3550 Marburg voz. Dr. Albrecht Salzer Fan cheisches Institut Universitit Zarich Winterthurer Str. 190 CH-8057 Zarich Jess, authors and publisher do not warrant the informa: carefully produced. Neverthe! This book wan carefully PeDOiE of errors. Readers are advised to Keep in mind that sta tom contained er cedura details oF other tems may inadvertently be inaccurate ements, data, , 2nd edition 1992 Published jointly by : VCH Verlagsgeselischaft mbH, Weinheim (Federal Republic of Germany) VCH Publishers Inc., New York, NY (USA) Editorial Director: Karin von der Saal Production Manager: Dipl.-Wirt.-Ing. (FH) Bernd Riedel Cover design: TWI, H. Weisbrod, D-6943 Birkenau Library of Congress Card No. applied for A catalogue record for this book is available from the British Library Die Deutsche Bibliothek ~ CIP-Einheitsaufnahme Eschebroch, Christoph: reanometallics : a concise introduction / Christoph Ekchenbroich Albrecht Salzer. ~ 2, rev. ed. Weinheim : fen York: Bae Cambridge : VCH, 1992 . cht.: Organometallche ISBN 3.527.28165-7 (Weinheim ..) a ISBN 0-89573-984-4 (New York) | Ne: Salzer, Albrecht: © VCH Verlagsgeselt ee feseltchafl mbH, D-6940 Weinheim (Federal Republic of Germany), 1992 on acid-free and low-chlorine paper All rights reserved (i part of this book eserved (includ ' inary ing those of translation into other ges) si sored Cig to aa ito : chine 7 ty ther erating, microfilm, or any other meng 7 nor ibd ort a machi 5 ane ‘when not {ct Permission from the publishers. Registered names, t book, even when Specifically marked as such, are not to be considered ion: Graphischer Betti : Graphischer Renin nie Konrad ‘Til 7 bindin Graphite ge Konrad Tauck, DOORN Konrad Thitseh, D-8700 WirsburgPreface to the Second Edition To revise, according to the Oxford American Dictionary, means to reexamine-and alter or correct. That is what we have done in this Second Edition which is characterized by elimination of errors, substitution of old examples with new ones, which illustrate certain statements more effectively, and addition of recent findings which are apt to become landmarks. From the last category, the following entries should be mentioned: the fundamental new main-group clement clusters R4B,, R,Al2; , and Cpt Alj, the hete- rocycle tellurepin; the first stable carbonyl complex of silver, Ag(CO) [B(OTeF.),}; the coordination of buckminsterfullerene to platinum; the unsupported Co=Co double bond in Cp*Co=CoCp*; and the stabilization of the disilylene Me,Si, through coordi- nation to tungsten (the cover molecule). Further important additions include mention of homogeneous Ziegler-Natta type catalysts based on Cp,ZrMe* derivatives, the pre- scription of how to arrive at the “magic numbers” which are supposed to govern cluster geometries, an extension of the section on CH activation, and a very brief treatment of organolanthanoid chemistry, which concludes the final chapter of the book. Allin all, we have made more than a hundred small changes, overt and covert, which may escape immediate detection since we have kept the format of the book virtually un- changed (A Concise Introduction). However, in order to lure the reader into looking up further details of interesting results, we now give in the author index. the complete literature citations of work referred to in the text. Once again, we thank our publisher for splendid cooperation, in particular Karin -von der Saal, who in her gentle but persistent way helped to complete the job in time: Apart from ourselves, no one read the manuscript; so nobody else is to blame for the remaining errors and omissions. Ch. Elschenbroich: November ‘A Salzer Marburg 1991 GermanyPreface to the First Edition The present volume Is the translation of the cassie eaten haw Of Our: text present YON gine kurze Einfihrung”. corrections and a few results of yepy -Organometallchemic | ® the body was left unchanged. Y vay were included but otherwise the rchanged. recent a ve treatise ona branch of chemistry still be called “concise”? On the other: Can a 500 page ff only 20 pages covering transition-metal olefin complexes certaj sain Petal short This contrast illustrates the dilemma encountered if one sets nahin ‘neal the whole of organometallic chemistry 1n a single volume of tolerablesige. The book developed from an introductory course (one semester. about 30 lectures) on organometallic chemistry for students confronted with the field for the first time. The material covered is a mixture of indispensible basic facts and selected results of most recent vintage. Attempts to systematize organometallic chemistry by relating molecular structures to the number and nature of the valence electrons are presented as are appli- cations of organometallics in organic synthesis and in industrial processes basedon homogeneous catalysis. An apparent omission is the absence of a chapter specifically dealing with organometallic reaction mechanisms. It is our contention, however, that mechanistic organometallic chemistry has not yet reached the stage which would warrant a short overview from which useful generalizations could be drawn by the beginner. Note, for example, that even reactions as fundamental as metal carbonyl substitution are currently under active investigation, the intermediacy of 17 or 19 valence electron species opening up new possible pathways. Interspersed within the text, however, the reader finds several com- ments and mechanistic proposals ranging from well established kinetic studies to catal- ysis loops which at times have more the character of mnemotechnic devices than of kinetic schemes based on experimental evidence. Detailed mechanistic considerations ara paaiiiel to the second act of the study of organometallic chemistry and several of material with ‘Which te carey organotransition metal compounds, offer a wealth We have structured the text in the ‘raditional way ~ following the periodic table for main-group element organometallics and Oe temo ligand for transition-metal complenes whic an according to the nature of the | : from the Chapters 16 and ya ie ne find most suitable for an introduction. specialized material is freee etal -metal bonds, clusters, catalysis) somewhat more Teferencing would be ina tii 7 sections called “Excursions”. Rigorous s¢ survey (300 odd entries) ie gi ‘ate in a text of the present scope. At the end, @ lite key papers, includin, is given which leads the reader to important review articles authors names are liked classics in the field. Furthermore, in the running hates the year of the disconge son's sesetibed whereby the form (Author, yea) year R) the appearance of te usually in a short communication, and the form ( Tespective full paper or review. The complete cit PPropiPreface vu then be easily retrieved via consultation of Chemical Abstracts. A desired side-effect is to familiarize the student with author's names and their fields of endeavor. The many coworkers, who actually did the work, may forgive us that only the name of the respec- tive boss is given. Among our own coworkers who helped to bring this English Edition to completion, the native speakers Pamela Alean (Great Britain, now u resident of Ziirich, Switzerland) and James Hurley (USA; resident of Marburg, Germany) stand out. They went a long way to eliminate our worst excesses of “Gerglish”. The bulk of the structural formulae was drawn by one of the authors (A.S.) thereby keeping things in the right perspective and making the book easy to use. Monika Scheld, Marburg. helped with the preparation of the indexes and by checking the cross references. We are grateful to the editor Dr. Michael Weller and the production manager Bernd Riedel (both of VCH Publishers) for a pleasant form of cooperation and their toleration of several last-minute changes. Finally, the authors mutually acknowledge their unflagging support during the various stages of the enterprise. Ch. Elschenbroich March A. Salzer Marburg 1989 Zirich Germany Switzerland