Water-Induced Switching in Selectivity and Steric Control of Activity in Photochemical CO Reduction Catalyzed by RhCp*(bpy) Derivatives.

Photocatalytic reduction of CO to formic acid (HCOOH) was investigated in either organic or aqueous/organic media by employing three water-soluble [RhCp*(LH)Cl] (LH = n,n'-dihydroxy-2,2'-bipyridine; = 4, 5, or 6) in the presence of [Ru(bpy)], 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[]imidazole (BIH) and triethanolamine (TEOA). Through studying the electron-donating effects of two hydroxyl groups introduced into the bipyridyl ligand, we found that the substituent positions greatly affect both the catalytic efficiency and selectivity in CO reduction. More importantly, the HCOOH selectivity shows a dramatic increase from 14 to 83% upon switching the solvent media from pure organic to an aqueous/organic mixture, where the H selectivity shows a reverse phenomenon. The enhanced HCOOH selectivity and the drastic decrease in the H yield are well rationalized by the fact that the catalytic CO hydrogenation is not only driven photochemically via the attack of Rh(H)Cp*(LH) on CO but also partly bypassed by a dark H addition reaction yielding [Rh(H)Cp*(L)] from [RhCp*(L)Cl], which was also separately investigated under dark conditions. A combination of experimental and theoretical approaches was made to clarify the p values of catalyst intermediates together with the abundant species responsible for the major catalytic processes. Our DFT studies unveil that the exceptionally large structural strain given by the steric contacts between the 6,6'-dihydroxyl groups and the Cp* moiety plays a significant role in bringing about an outstanding catalytic performance of the 6,6'-substituted derivative. The intrinsic reaction coordinate calculations were carried out to clarify the mechanism of hydride transfer steps leading to generating formate together with the heterolytic H cleavage steps leading to afford the key hydridorhodium intermediates. This study represents the first report on the water-induced high selectivity in CO-to-HCOOH conversion, shedding new light on the strategy to control the efficiency and selectivity in the catalysis of CO reduction.