A silyl(silylene) iron complex, Cp*Fe(CO)(=SiMes2) SiMe3 (1), which was prepared by the photoreaction of Cp*Fe(CO)2Me (2) with hydrodisilane Mes 2MeSiSiMe2H (3), reacted with nitriles RCN (R = Ph, Me) at 80°C to afford a mixture of a disilanyl isocyanide complex Cp*Fe(CO)(R)(CNSiMe2SiMes2Me) (5a, R = Ph; 5b, R = Me) and a pair of diastereomers of Cp*Fe(CO)(R)(CNSiMesMeSiMesMe 2) (6a, R = Ph; 6b, R = Me). The molecular structure of 5a was determined by X-ray crystallography. On the other hand, when the photoreaction of 2 with 3 was performed in the presence of benzonitrile, acetonitrile, or acetonitrile-d3, at ca. 5°C, only the disilanyl isocyanide complex 5a, 5b, or 5b-d3 was obtained as a single product. The formation of these disilanyl isocyanide complexes is understood by the action of coordinatively unsaturated disilanyliron(II) intermediates Cp*Fe(CO) SiMe2SiMes2Me, etc., which are transiently generated by thermal isomerization of 1 or photoreaction of 2 with 3, to incoming nitriles. The C-C bond of the nitrile ligand is activated through migration of the disilanyl group to the nitrogen atom of nitriles.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry