Masked silylene complexes Cp*(IXy-H)(H)RuSiH<sub>2</sub>R (R =
Mes (<b>3</b>) and Trip (<b>4</b>); IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene;
“IXy-H” is the deprotonated form of IXy) exhibit metallosilylene-like
(L<sub><i>n</i></sub>M–Si–R) reactivity, as
observed in reactions of nonenolizable ketones, enones, and tosyl
azides, to give unprecedented silaoxiranyl, oxasilacyclopentenyl,
and silaiminyl complexes, respectively. Notably, these silicon-containing
complexes are derived from the primary silanes MesSiH<sub>3</sub> and
TripSiH<sub>3</sub> via activation of all three Si–H bonds.
DFT calculations suggest that the mechanism of formation for the silaoxiranyl
complex Cp*(IXy)(H)<sub>2</sub>Ru–Si(OCPh<sub>2</sub>)Trip
(<b>6</b>) involves coordination of benzophenone to a silylene
silicon atom, followed by a single-electron transfer in which Si-bonded,
non-innocent benzophenone accepts an electron from the reactive, electron-rich
ruthenium center. Importantly, this electron transfer promotes an
unusual 1,2-hydrogen migration to the resulting, more electron-deficient
ruthenium center via a diradicaloid transition state