Molecular recognition in Mn-catalyzed C-H oxidation. Reaction mechanism and origin of selectivity from a DFT perspective.

ABSTRACT: Experimental studies have shown that the C-H oxidation of Ibuprofen and methylcyclohexane acetic acid can be carried out with high selectivities using [(terpy')Mn(OH(2))(mu-O)(2)Mn(OH(2))(terpy')](3+) as catalyst, where terpy' is a terpyridine ligand functionalized with a phenylene linker and a Kemp's triacid serving to recognize the reactant via H-bonding. Experiments, described here, suggest that the sulfate counter anion, present in stoichiometric amounts, coordinates to manganese in place of water. DFT calculations have been carried out using [(terpy')Mn(O)(mu-O)(2)Mn(SO(4))(terpy')](+) as a model catalyst, to analyze the origin of selectivity and its relation to molecular recognition, as well as the mechanism of catalyst inhibition by tert-butyl benzoic acid. The calculations show tha

SUBMITTER: Balcells D 

PROVIDER: S-EPMC2908378 | biostudies-literature | 2009 Aug

REPOSITORIES: biostudies-literature