In the pursuit of homogeneous methane functionalization catalysts, we are using calculated free energies (DFT with Poisson-Boltzmann continuum solvation) to (1) discover relationships between catalyst composition and barriers to C-H activation and M-CH3 functionalization and (2) identify specific designs most promising for experimental work.  Among more electrophilic metals, we are studying phosphine complexes of iridium to identify combinations of ligand, counterion (hydroxide, carboxylates, halides) and pH that allow both SN2 functionalization of Ir-CH3 bonds and C-H activation via thermally accessible barriers in protic media.  With more nucleophilic, d6 complexes of Ru, Os and Re, we have studied the dependence of substitution, insertion and base-assisted C-H activation barriers on hydroxide concentration, electron-donating ligand substituents, and metal.  We then studied the electrophilic attack of metal-oxo bonds on the resulting M-CH3 intermediates.

Free energy calculations for designing methane functionalization catalysts

239th National Meeting (2010)

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