Computational Study of CO₂ Reduction Catalyzed by Iron(I) Complex at Different Spin States: Cooperativity of Hydrogen...

To explore alternative approaches to the CO₂ reduction to formate and provide an insight into the spin state effect on the CO₂ reduction, we theoretically designed a kind of low-valence iron(I) model complex, whose doublet, quartet, and sextet states are denoted as Fe(I), Fe(I), and Fe(I), respectively. This complex is featured with an iron(I) center, which bonds to a 1,2-ethanediamine (en) and a 2-hydroxy-biphenyl group. Reaction mechanisms for the CO₂ reduction to formate catalyzed by this iron(I) model complex were explored using density functional theory (DFT) computations. Studies showed that the univalent iron(I) compound can efficiently fix and activate a CO₂ molecule, whereas its oxidized forms with trivalent iron(III) or bivalent iron(II) cannot activate CO₂. For the iron(I) compound, it was found that the lowest spin state Fe(I) is the most favorable for the CO₂ reduction as the reactions barriers involving Fe(I), Fe(I), and Fe(I) are 25.6, 37.2, and 35.9 kcal/mol, respectively. Yet, a photosensitizer-free visible-light-mediated high-low spin shift from Fe(I) and Fe(I) to Fe(I) is likely through the reverse intersystem crossing (RIC) because the Fe(I) and Fe(I) compounds have strong absorption in the visible-light range. Notably, the synergistic interaction between the hydrogen bonding from the auxiliary hydroxyl group in the 2-hydroxy-biphenyl moiety to CO₂ and an intermediate five-membered ring promotes the proton transfer, leading to the formation of the -COOH moiety from CO₂ and the Fe-O bond. With the addition of H₂, one H₂ molecule is split by the Fe-O bond and thus serves as H atom sources for both the CO₂ reduction and the recovery of the auxiliary hydroxyl group. The present theoretical study provides a novel solution for the challenging CO₂ reduction, which calls for further experimental verifications.