We have predicted free energy surfaces (using DFT and continuum solvation) of complete catalytic cycles for the oxidation of methane catalyzed by homogeneous rhodium complexes in order to determine compositions which minimize global activation barriers.  CH activation by Rh(I) and Rh(III) were considered, as well as C-X bond formation via traditional SN2 attack and electrophilic attack on the Rh-CH3 intermediate.  PNP and CNC pincer ligands were substituted to vary electronic and steric properties.  Trifluoroacetic acid and aqueous solutions of chloride and bisulfate were considered as solvents and provided coordinating anions.  Composition-activity relationships are discussed.

Free energy surfaces for developing homogeneous rhodium catalysts for methane oxidation

243rd National Meeting (2012)

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