We have synthesized and structurally characterized the neutral iron silylene complexes, Cp*(iPr2MeP)FeH=SiHR (R = DMP, Trip) by treatment of a 16-electron iron mesityl complex, Cp*(iPr2MeP)FeMes with primary silanes (DMPSiH3, TripSiH3). The electronic and geometric structures of these complexes at room temperature are extremely fluxional and exhibit both Fe-H/Si-H exchange processes and the related thermal population of a triplet state; both of these processes are frozen out at lower temperature. We compare the structural and spectroscopic properties of these complexes to those of isostructural Ru and Os neutral silylene complexes which our group previously reported. The iron silylene complexes also mediate C-H activation reactions (intramolecular for R = DMP, intermolecular for R = Trip) to give either the cyclosilated complex, Cp*(iPr2MeP)FeH2SiH(κ2-C,C-DMP), from activation of an ortho-methyl substituent on a mesityl flanking group or the iron silyl complex Cp*(iPr2MeP)FeH2SiH2Trip from activation of 2 equivalents of toluene.

Synthesis, structure, and reactivity of hydridosilylene complexes of iron

251st National Meeting (2016)

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