Cp(CO)2FeSiMe2Cl (1) with LiNMe2 provides a ready access to the iron silylamine Cp(CO)2FeSiMe2NMe2 (2). In addition the binuclear complex [η5-(Me2NSiMe2C5H4)(CO)2Fe]2 (3) is obtained, the formation of which involves an anionic shift of the aminosilyl group from the iron atom to the η5-coordinated cyclopentadienyl ring. An analogous silylmigration is responsible for the conversion of 2 or Cp(CO)2FeSiMe2H
A hydride abstraction from the hydrosilyliron complexes Cp(OC)(2)FeSiR2H (Cp = eta(5)-C5H5, R = p-tolyl (la), Me (1b)) in CD3CN afforded cationic silyleneiron complexes [Cp(OC)(2)Fe=SiR2(NCCD3)][13(Ar-f)(4)] (Ar-f = 3,5-bis(trifluoromethyl)phenyl, R = p-tolyl (2a), Me (2b)). The cationic silylene complexes 2 catalyzed hydrosilylation of aldehydes and ketones with 1 to give the corresponding alkoxysilyliron complexes 3-5 in moderate to high yield.