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Rhodium Bis(quinolinyl)benzene Complexes for Methane Activation and Functionalization
Author(s) -
Fu Ross,
O'Reilly Matthew E.,
Nielsen Robert J.,
Goddard III William A.,
Gunnoe T. Brent
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405460
Subject(s) - surface modification , rhodium , chemistry , catalysis , benzene , methane , density functional theory , photochemistry , inorganic chemistry , organic chemistry , computational chemistry
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 CH 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 S N 2 and S R 2 attack.