Exploring the intermediates of photochemical CO2 reduction: reaction of Re(dmb)(CO)3 COOH with CO2Electronic supplementary information (ESI) available: Complete ref. 16, data from computed stationary points, experimental methods, and spectroscopic data from experiment. See DOI: 10.1039/c2cc32288a

We have investigated the reaction of Re(dmb)(CO) 3 COOH with CO 2 using density functional theory, and propose a mechanism for the production of CO. This mechanism supports the role of Re(dmb)(CO) 3 COOH as a key intermediate in the formation of CO. Our new experimental work supports the proposed scheme. An explicit pathway for the reactivity of CO 2 with Re(dmb)(CO) 3 COOH is proposed from theoretical studies and further supported by experiment.