[(tBu2PCH2SiMe2)2N]RuCH3: the origin of extremely facile, double H-C(sp3) activation generating a "hydrido-carbene" complex.
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.
Ingleson
Michael J
MJ
Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN, USA.
Yang
Xiaofan
X
Pink
Maren
M
Caulton
Kenneth G
KG