Abstract
Metallacycles of transition metals are generally of great interest because of their multifaceted structural chemistry and they are often discussed as key intermediates in multiple catalytic processes, whereupon recent studies are dealing with the participation of metallacycles in polymerization as well as oligomerization reactions. Synthesis and characterization of the titanocene bis(trimethylsilyl)acetylene complex Cp2Ti(η2-Me3SiC2SiMe3) paved the way towards the discovery of three-membered metallacyclopropenes of Group 4 metals (titanium, zirconium, and, later, hafnium) having their own history which is strongly connected with the names of M. E. Vol´pin and his co-workers. Starting from these compounds the very unusual ring-strained “all-C”-five-membered metallacyclocumulenes, metallacyclopentynes, and metalla-cycloallenes of Group 4 metals were obtained and characterized having all their roots in Vol´pin´s chemistry. This mini review gives an overview of these unusual molecules as well as some more common molecules like metallacyclopentanes, metallacyclopentenes, and metalla-cyclopentadienes. Very recently instead of these “all-C”-metallacycles the analogous heteroring systems (with N, S, O atoms instead of C) as well as the smaller four-membered metallacycles became the focus of our interest.
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Dedicated to the memory of Academician M. E. Vol´pin.
Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), 29a Albert-Einstein-Straße, 18059 Rostock, Deutschland.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2577—2582, November, 2014.
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Rosenthal, U. Metallocene-made mad metallacycles in synthesis and catalysis. Russ Chem Bull 63, 2577–2582 (2014). https://doi.org/10.1007/s11172-014-0781-6
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DOI: https://doi.org/10.1007/s11172-014-0781-6