Organometallics 2010, 29, 1–1 DOI: 10.1021/om900979t
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Introduction to the Review by H. Schmidbaur and A. Schier in This Issue of Organometallics The molecule on the cover of this issue of Organometallics is the gold(I) chloride complex of cis-cyclooctene, C8H16 3 AuCl. This compound was one of the first of the olefin-AuCl π-complexes prepared by Rudolf H€ uttel and his students at the University of Munich in the mid-1960s. Its molecular and crystal structures were reported some 20 years later by Dell’Amico and Calderazzo of the University of Pisa and Dantona, Str€ ahle, and Weiss of the University of T€ ubingen (Organometallics 1987, 6, 1207), who prepared it by the reaction of a toluene/dichloromethane suspension of AuCl(CO) with an excess of a 9:1 mixture of cis- and trans-cyclooctene at -30 °C. In their review, Professor Hubert Schmidbaur and Dr. Annette Schier of the Technical University of Munich give a thorough discussion of the complexes of gold in its various oxidation states with unsaturated hydrocarbons: alkenes (of which our cover molecule is a representative), alkynes, and arenes. Preparative aspects are covered, but the emphasis is on structure and bonding. This review comes at an opportune time when gold complexes have begun to play an important role in organic catalytic processes, replacing the toxic mercuric salts and the more expensive platinum and palladium complexes as catalysts in some important organic transformations. Professor Schmidbaur and Dr. Schier, as authors of an earlier review in this journal (Organometallics 2008, 27, 2361), have already been introduced to our readers in the Editor’s Page for that paper. Professor Schmidbaur has been for many years a leader in the inorganic and organometallic chemistry of gold. In his various other areas of research we also find interesting papers in which gold plays an important role. In his early (1966) work on heterosiloxanes, investigations on gold derivatives of siloxanes with Si-O-Au bonds were reported. In his long-term research in organophosphorus ylide chemistry, he introduced important new gold chemistry (reviews in Accounts of Chemical Research in 1975 and Angew. Chem. Int. Ed. in 1983). Professor Schmidbaur became thoroughly immersed in inorganic/organometallic gold chemistry when he wrote the Gmelin Handbook of Inorganic Chemistry volume on organogold compounds (published in 1980). An inevitable result of writing the Gmelin was that, as he says, “it gave me a much broader scope and vision for gold research.” Interest in theoretical aspects of gold chemistry, in particular the importance and consequences of relativistic effects, led Professor Schmidbaur to a long-term collaboration with Professor Pekka Pyykk€ o of the University of Helsinki and resulted in very interesting experimental studies relating to the aurophicity concept, weak Au 3 3 3 Au interactions of the strength of hydrogen bonds which have significant structural consequences. Of special interest have been Professor Schmidbaur’s compounds containing “gold-plated” carbon atoms, salts of the unprecedented and spectacular hypercoordinate carbocations [(Ph3P)Au]5Cþ and [(Ph3P)Au]6C2þ. Peraurated cationic derivatives of nitrogen, e.g., [(Ph3P)Au]5N2þ, of phosphorus, e.g., {[(Ph3P)Au]4P-Au-P[Au(PPh3)]4}3þ, and of the chalcogens also were prepared in this broad-ranging study. An excellent summary of this work is found in a 1995 Chemical Society Reviews article. Professor Schmidbaur has published some 350 papers in which some aspect of gold chemistry is discussed, many of them with Dr. Schier as the crystallographer among the coauthors. In view of all this work, as well as that of others, it is obvious that gold chemistry holds considerable promise of many more new discoveries of theoretical and practical importance. As always, I am grateful to Professor Arnold L. Rheingold for the cover figure.
Dietmar Seyferth Editor Emeritus
r 2009 American Chemical Society
Published on Web 11/19/2009
pubs.acs.org/Organometallics
