938160-71-5Relevant articles and documents
Competing reactions of hypercoordinate silicon dichelates
Kalikhman, Inna,Gostevskii, Boris,Kertsnus, Evgenia,Deuerlein, Stephan,Stalke, Dietmar,Botoshansky, Mark,Kost, Daniel
, p. 1029 - 1034 (2008)
Neutral hexacoordinate silicon complexes derived from hydrazide chelating ligands with imino-donor groups, and their pentacoordinate ionic dissociation products, undergo facile intramolecular aldol-type condensation catalyzed by their chloride counterion leading to formation of a third chelate ring. In analogous silacyclobutane dichelates, in the absence of halide counterion, a similar uncatalyzed rearrangement takes place, accompanied by opening of the four-membered ring. In the absence of a-protons necessary for the condensation, the four-membered ring residue adds directly to one of the imino-carbon atoms forming a new C-C bond and closing a different chelate ring. This latter addition to the imino carbon is the preferred reaction pathway, even in the presence of 12 α-protons, when cyanide ion replaces the chloride counterion and acts as nucleophile. The cyanide reactivity is rationalized in terms of the HSAB concept. An unusual intramolecular rearrangement involving the migration of a t- butyl group from silicon to carbon, while enabling the unprecedented attachment of a third hydrazide chelating agent, leading to a hexacoordinate trichelate complex, is presented. Copyright
