Landmarks in Organo-Transition Metal Chemistry Profiles in Inorganic Chemistry

Landmarks in Organo-Transition Metal Chemistry Profiles in Inorganic Chemistry Series Editor: John P. Fackler, Texas A & M University, College Station, Texas Current Volumes in this Series: Landmarks in Organo-Transition Metal Chemistry: A Personal View Helmut Werner From Coelo to Inorganic Chemistry: A Lifetime of Reactions Fred Basolo A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher. Helmut Werner Landmarks in Organo-Transition Metal Chemistry A Personal View 13 Helmut Werner Institute of Inorganic Chemistry University of Wu¨ rzburg Germany ISSN: 1571-036X ISBN: 978-0-387-09847-0 e-ISBN: 978-0-387-09848-7 DOI 10.1007/978-0-387-09848-7 Library of Congress Control Number: 2008940859 # Springer ScienceþBusiness Media, LLC 2009 All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer ScienceþBusiness Media, LLC, 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks, and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed on acid-free paper springer.com To Monika, Andreas, and Annemarie And in Loving Memory of Helga Foreword Organometallic chemistry has witnessed an exponential growth in the past half decade, and today is represented at its frontiers by the second edition of a multi- volume text, two major journals and a plethora of monographs. Helmut Werner, a pioneer who has contributed extensively to the field, now offers us a personal view of important areas of transition metal chemistry. It is unusual in that it provides an historical perspective on some of the more significant developments in this area. He writes both with a great generosity of spirit and an obvious love of the subject. It is evident that both for him, and now his readers, it is not only the science, but also its protagonists, that are the focus of much attention. The first two chapters provide interesting information on Helmut’s family and scientific background, culminating in his Wu¨ rzburg C4 professorship (since 1975); he has mentored 110 Ph.D. students and 40 postdoctoral and visiting scientists. He continues in Chap. 3 to provide an account of the birth of the subject and its development in the nineteenth century. Subsequent chapters deal with metal carbonyls and derived clusters, the discovery of ‘‘sandwich’’ compounds, triple-decker analogues, metal–ethene complexes and their congeners, metal carbenes and carbynes, and finally metal alkyls and aryls. Each chapter has ample references. Helmut’s account is exceedingly modest; from around 800 citations, less than 20 are to his own contributions. The text is well illustrated with formulae, reaction schemes, biographies and photographs. The work is of very high quality and the author is to be congratulated on having given us a very informative and eminently readable and enjoyable book. He clearly has a profound knowledge of the subject and, as one of its leading practitioners, offers his readers a unique overview. I commend it with confi- dence and much enthusiasm. July 2008 Michael Lappert vii Series Preface A renaissance in the field of inorganic chemistry began in the middle of the twentieth century. In the years following the discoveries of A. Werner and S. M. Jørgensen at the turn of the century, the field was relatively inactive. The publication of Linus Pauling’s Nature of the Chemical Bond in 1938 and World War II shortly thereafter launched this renaissance. The war effort required an understanding of the chemistry of uranium and the synthetic actinide elements that were essential to the production of the atom bomb. There was also a need for catalysts to produce rayon, nylon, synthetic rubber, and other new materials for the war effort. As a result, many gifted chemists applied their talents to inorganic chemistry. Profiles in Inorganic Chemistry explores the roles some of the key contributors played in the renaissance and development of the field. Some of the early leaders in this reawakening are now deceased. Pioneers included John Bailar at the University of Illinois, W. Conard Fernelius, at Pennsylvania State University, and Harold Booth at Western Reserve Univer- sity, who with some others, started the important series entitled Inorganic Syntheses. Several inorganic chemistry journals were born, as were various monograph series including the Modern Inorganic Chemistry series of Springer. Geoffrey Wilkinson, who along with E. O. Fischer was the first inorganic chemist since Werner to win the Nobel prize, started his career at Harvard in about 1950 but later that decade moved to the University of London’s Imperial College. By then, Ron Nyholm already was building a strong inorganic pro- gram at the University of London’s University College. Physical and mathematical concepts including group theory gave inorganic chemists new tools to understand bonding, structure, and dynamics of inorganic molecules. Fischer, Wilkinson, and their contemporaries opened up a new subfield, organometallic chemistry, out of which many metal-based catalysts were developed. It was soon realized that many inorganic minerals play essential roles as catalysts in living systems. As a result, another subfield, bioinor- ganic chemistry, was born. The discipline of inorganic chemistry today includes persons of many different walks of life, some creating new material and catalysts, others studying living systems, many pondering environmental concerns ix x Series Preface with elements such as tin, mercury, or lead, but all focusing on questions outside the normal scope of organic chemistry. Organic chemistry has enjoyed a long history as a great science, both in Europe and the United States. During the past 15 years or so, many of the U.S. contributors have produced interesting autobiographies as part of an American Chemical Society series entitled Profiles in Inorganic Chemistry. There is also, however, a need to have students and scientists of inorganic chemistry understand the motivating forces that lead prominent living inorganic chemists to formulate their ideas. I am grateful that Springer has undertaken to publish this series. These profiles in inorganic chemistry will portray the interesting and varied personalities of leaders who have contributed significantly to the renaissance of inorganic chemistry. College Station, TX John P. Fackler, Jr. Preface In the short period between December 1951 and February 1952, two papers appeared which laid the roots for what a few years later was called by Sir Ronald Nyholm The Renaissance of Inorganic Chemistry. Two research groups, working in completely different fields, reported the isolation of a seemingly simple iron compound of the analytical composition FeC10H10 which quite soon became the flagship of a new chemical discipline. It was not the composition of the new compound but its surprising and absolutely unexpected mole- cular structure that stimulated both experimental and theoretical chemists. While in the nineteenth and even in the first half of the twentieth century, it usually took decades before an epoch-making idea such as the cyclic structure of benzene, the tetrahedral configuration of methane, or Alfred Werner’s con- cept of coordination compounds has been accepted, the synthesis and structural elucidation of bis(cyclopentadienyl)iron FeC10H10 – later called ferrocene – initiated immediately a research avalanche for which there is almost no pre- cedent. In less than 20 years, not only metal compounds containing planar three-, four-, five-, six-, seven- and eight-membered ring systems were prepared, but at the same time also the chemistry of compounds with metal–carbon double and triple bonds was brought to light. The synthetic techniques together with the newly emerging analytical tools, in particular IR and NMR spectro- scopy, offered the opportunity to follow the course of a chemical reaction and thus to understand the mechanism of the process. This also led to the rebirth of the field of homogeneous catalysis, and it is only fair to say that without the pioneering work in the 1950s and early 1960s on transition metal organome- tallics a number of important industrial processes such as the oxidation of ethene to acetaldehyde by the Wacker reaction, the synthesis of L-Dopa by the Monsanto process or the stereoselective polymerisation of olefins with the Brintzinger-type ansa-metallocenes as catalysts would not have been developed. When I started writing this book, it was exactly 50 years ago that I became acquainted with organo-transition metal chemistry. As an undergraduate at the University of Jena in the former Deutsche Demokratische Republik (‘‘East Germany’’), I attended a course in preparative inorganic chemistry and a junior colleague of Professor Franz Hein took care of the course. It was at this time, that Professor Ernst Otto Fischer visited Hein’s laboratory to inform him that, xi xii Preface based on his work at the Technische Hochschule in Mu¨ nchen, he was convinced that the unusual ‘‘polyphenylchromium compounds’’, reported by Hein mainly between 1919 and 1931, were indeed sandwich-type complexes. At first, Hein was irritated but after his coworkers proved that Fischer’s proposal was correct, he accepted the new ideas. Since I had the fortune to work for my Diploma thesis with Hein and for my Ph.D. thesis with Fischer, I became automatically involved in the rapid and breath-taking development of modern organometallic chemistry, and I remained caught and fascinated by this subject ever since.

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