title: Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization.
abstract: A series of rhodium(III) bis(quinolinyl)benzene (bisq(x)) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisq(x)) ligand candidates involving different functional groups to determine the impact on Rh(III)(bisq(x))-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is Rh(III) coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η(2)-benzene coordination mode of (bisq(x)) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.
authors.affiliation: Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125 (USA).
authors.forename: Ross
authors.initials: R
authors.lastname: Fu
authors.forename: Matthew E
authors.initials: ME
authors.lastname: O'Reilly
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Nielsen
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: T Brent
authors.initials: TB
authors.lastname: Gunnoe
keywords: CH activation; ab initio calculations; catalysis; methane functionalization; rhodium