title: Donor-Promoted 1,2-Hydrogen Migration from Silicon to a Saturated Ruthenium Center and Access to Silaoxiranyl and Silaiminyl Complexes.
abstract: Masked silylene complexes Cp*(IXy-H)(H)RuSiH2R (R = Mes (3) and Trip (4); IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; "IXy-H" is the deprotonated form of IXy) exhibit metallosilylene-like (LnM-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 MesSiH3 and TripSiH3 via activation of all three Si-H bonds. DFT calculations suggest that the mechanism of formation for the silaoxiranyl complex Cp*(IXy)(H)2Ru-Si(OCPh2)Trip (6) 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.
authors.affiliation: †Department of Chemistry, University of California, Berkeley, California 94720-1460 United States.
authors.forename: Hsueh-Ju
authors.initials: HJ
authors.lastname: Liu
authors.affiliation: §Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 United States.
authors.forename: Clark
authors.initials: C
authors.lastname: Landis
authors.affiliation: ‡Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, F-34095 Montpellier, France.|∥Laboratoire de Chimie Théorique, CNRS UMR 7616, UPMC Paris 6, 75005 Paris, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Raynaud
authors.affiliation: ‡Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, F-34095 Montpellier, France.
authors.forename: Odile
authors.initials: O
authors.lastname: Eisenstein
authors.affiliation: †Department of Chemistry, University of California, Berkeley, California 94720-1460 United States.
authors.forename: T Don
authors.initials: TD
authors.lastname: Tilley