title: [(tBu2PCH2SiMe2)2N]RuCH3: the origin of extremely facile, double H-C(sp3) activation generating a "hydrido-carbene" complex.
abstract: The four-coordinate compound [(tBu2PCH2SiMe2)2N]RuCH3 undergoes rapid double H-C(sp3) activation at -78 degrees C to generate a "hydrido-carbene" complex. DFT calculations suggest that the origin of the low barrier to methane elimination is an alpha-agostic interaction in the low-lying singlet state of the highly unsaturated (PNP)RuMe. The hydrido-carbene complex can be viewed as a "masked" resting state of the four-coordinate cyclometalated alkyl complex, [(tBu2PCH2SiMe2)N(Me2SiCH2P(tBu)(C(CH3)2CH2)]Ru, where hydride migration from metal to carbon occurs before any subsequent reactivity.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN, USA.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Ingleson
authors.forename: Xiaofan
authors.initials: X
authors.lastname: Yang
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton