Mechanistic study of the rhodium-catalyzed carboxylation of simple aromatic compounds with carbon dioxide† †Electronic supplementary information (ESI) available: Experimental details and crystallographic data in cif format. CCDC 1017905. For ESI and crystallographic data in CIF or other electronic formats see DOI: 10.1039/c6sc03838g Click here for additional data file. Click here for additional data file.

A detailed mechanism of the Rh(I)-catalyzed carboxylation of simple aromatic compounds via C–H bond activation was investigated. Kinetic studies with model compounds of the postulated key intermediates revealed that 14-electron complexes, RhMe(dcype) and RhPh(dcype), participated in the C–H bond activation step and the carboxylation step, respectively. Interestingly, the undesired carboxylation of RhMe(dcype) to give acetic acid was found to be much faster than the desired C–H bond activation reaction under stoichiometric conditions, however, the C–H bond activation reaction could occur under catalytic conditions. Careful controlled experiments revealed that C–H bond activation using RhMe(dcype) became competitive with its direct carboxylation under the condition that the concentration of CO2 in the liquid phase was rather low. This factor could be controlled to some extent by mechanical factors such as the stirring rate and the shape of the reaction vessel. The resting state of the rhodium species under catalytic conditions was found to be [RhCl(dcype)]2, and the proposed intermediates such as RhMe(dcype) and Rh(OBz)(dcype) were readily converted to the most stable state, [RhCl(dcype)]2, via transmetallation with [Al]–Cl species, thus preventing the decomposition of the active catalytic species.