Design, synthesis and photocatalytic activities of functionalized Re(I) bipyridine tricarbonyl complexes toward CO2 reduction and carboxylation

Natural metalloenzymes efficiently catalyze chemical transformations by precisely controlling the local environment around the active site, thereby enabling selective substrate activation and reaction control. This general concept has motivated extensive efforts to improve molecular catalysts by ligand modification and functionalization. In this work, we designed and synthesized functionalized derivatives of the fac -Re(2,2′-bipyridine)(CO) 3 Cl complex ( Re-1 ), which has long been recognized as a benchmark catalyst for photochemical CO 2 reduction, and which we have recently demonstrated to also catalyze the carboxylation of organic substrates with CO 2 . Using these complexes, we investigated how substituents on the bipyridine ligand affect photocatalytic activities in both CO 2 reduction and carboxylation reactions. All new complexes were fully characterized by single-crystal X-ray diffraction analysis as well as by spectroscopic and electrochemical methods. The introduction of electron-withdrawing functional groups induces clear changes in the electronic structures of the complexes, as evidenced by redshifts in their absorption spectra, CO stretching frequencies, and reduction potentials. In photocatalytic CO 2 reduction, the catalytic activities of the functionalized complexes depend strongly on these electronic properties, whereas in carboxylation reactions, all complexes show comparable catalytic performance regardless of the nature of the functional groups. Moreover, the present system also exhibits additional reactivities, including [2 + 2] dimerization and hydroacylation reactions. Collectively, this work reports the design, synthesis, and characterization of a new series of functionalized Re(I) complexes, and provides a useful experimental basis for understanding how ligand modification influences their properties and reactivity, thereby offering guidance for future development of Re-based molecular systems for CO 2 utilization. A series of rhenium bipyridine complexes bearing various functional groups were synthesized and investigated. Their electronic properties and catalytic activities for photocatalytic CO 2 reduction and alkene carboxylation were compared, providing insight into how ligand functionalization influences reactivity in CO 2 conversion systems. • Ligand-functionalized Re(I) tricarbonyl complexes were successfully synthesized. • New complexes were fully characterized by X-ray diffraction and several techniques. • Photocatalytic CO2 reduction and carboxylation with CO2 were studied. • The reactivities for additional reaction pathways were revealed.