Metal-mediated alkane functionalization requires catalyzing C-H cleavage and carbon-heteroatom bond formation, each of which pose high, potentially rate-limiting barriers. To complement the traditional nucleophilic attack mechanism for functionalizing M-CH<sub>3</sub> bonds, we have used computed free energy surfaces to develop the attack of electrophiles on metal-carbon bonds. Recently we described the conversion of a vanadium-phenyl bond to phenoxide via migration of the phenyl group to a separate vanadate oxo group. This formally homolytic M-C bond cleavage results in the one-electron reduction of both vanadium centers. We predict that some one-electron oxidants will allow this mechanism to be transferred to late transition metals compatible with non-radical methane oxidation. Iridium-methyl bonds, however, are less polar than those of Group 10 metals and stronger than those of 1st and 2nd row metals. We find their functionalization is likely to begin with attack at the C-H bonds.

Metal-carbon bond functionalization in the context of methane oxidation

251st National Meeting (2016)

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