Photocatalytic reduction of CO<sub>2</sub> using cis,trans-[Re(dmbpy)(CO)<sub>2</sub>(PR<sub>3</sub>)(PR′<sub>3</sub>)]<sup> </sup> (dmbpy = 4,4′-dimethyl-2,2′-bipyridine).
Photocatalysis of biscarbonylrhenium complexes cis,trans-[Re(dmbpy)CO)2(PR3) (PR′3)] (dmbpy = 4,4′-dimethyl-2,2′-bipyridine: R, R′ = Ph (1a ); p-FPh (1b ); R = Ph, R′ = OEt (1c ); R, R′ = O-i-Pr (1d )) is reported for the first time. The rhenium complexes with two triarylphosphine ligands (1a , 1b ) efficiently photocatalyzed CO2 reduction with triethanolamine as a sacrificial donor. On the other hand, the complexes with one or two trialkylphosphite ligand(s) (1c , 1d ) had low photocatalytic abilities under the same reaction conditions.