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Keywords:

  • silylene complex;
  • silyl(silylene) complex;
  • base-stabilized bis(silylene) complex;
  • 1,3-migration;
  • 1,2-migration

Abstract

In 1987, two research groups published the first-ever reports on the synthesis of silylene complexes and presented structural evidence. Since then, a range of synthetic methods have been developed and a number of silylene complexes have been prepared. In 1988, we reported on the first base-stabilized bis(silylene) complexes that can be regarded as being masked silyl(silylene) complexes. These complexes occupy a unique position among silylene and silyl(silylene) complexes in that they provide a convenient tool for studying the reactivity of coordinated silylenes. They are stable enough to be isolated, but the bond between the silylene silicon atom and the internal base can easily be cleaved by thermal perturbation to generate real silyl(silylene) complexes. To date, a number of base-stabilized bis(silylene) complexes have been prepared in which the central metals range from group 5 to group 9. Only two base-free silyl(silylene) complexes have been prepared. One is prepared by reacting a platinum complex with a stable silylene; the other is produced by the photolysis of a tungsten complex in the presence of a hydrodisilane. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 291–306, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10034