DFT insights into the photocatalytic reduction of CO2 to CO by Re(I) complexes: the crucial role of the triethanolamine "magic" sacrificial electron donor

Abstract

The reaction mechanism for the photocatalytic reduction of CO₂ to CO catalyzed by the [Re(en)(CO)₃Cl] complex in the presence of triethanolamine, R₃N (R = CH₂CH₂OH) abbreviated as TEOA, in DMF solution was studied in-depth with the aid of DFT computational protocols by calculating the geometric and free energy reaction profiles for several possible reaction pathways. The reaction pathways studied start with the "real" catalytic species [Re(en)(CO)₃], [Re(en)(CO)₃]^- and/or [Re(en)(CO)₂Cl]^- generated from the excited triplet T1 state upon single and double reductive quenching by a TEOA sacrificial electron donor or photodissociation of a CO ligand. The first step in all the catalytic cycles investigated involves the capture of either CO₂ or the oxidized R₂NCH₂CH₂O˙ radical. In the latter case, the CO₂ molecule is captured (inserted) by the Re-OCH₂CH₂NR₂ bond forming stable intermediates. Next, successive protonations (TEOA also acts as a proton donor) lead to the release of CO either from the energy consuming 2e^- reduction of [Re(en)(CO)₄]⁺ or [Re(en)(CO)₂Cl]⁺ complexes in the CO₂ capture pathways or from the released unstable diprotonated [R₂NCH₂CH₂OC(OH)(OH)]⁺ species regenerating TEOA and the catalyst. The CO₂ insertion reaction pathway is the favorable pathway for the photocatalytic reduction of CO₂ → CO catalyzed by the [Re(en)(CO)₃Cl] complex in the presence of TEOA manifesting its crucial role as an electron and proton donor, capturing CO₂ and releasing CO.