Activating the Fe(I) State of Iron Porphyrinoid with Second-Sphere Proton Transfer Residues for Selective Reduction of CO₂ to HCOOH via Fe(III/II)–COOH Intermediate(s)
2021
Amanullah, Sk | Saha, Paramita | Dey, Abhishek
The ability to tune the selectivity of CO₂ reduction by first-row transition metal-based complexes via the inclusion of second-sphere effects heralds exciting and sought-after possibilities. On the basis of the mechanistic understanding of CO₂ reduction by iron porphyrins developed by trapping and characterizing the intermediates involved (J. Am. Chem. Soc.2015, 137, 11214), a porphyrinoid ligand is envisaged to switch the selectivity of the iron porphyrins by reducing CO₂ from CO to HCOOH as well as lower the overpotential to the process. The results show that the iron porphyrinoid designed can catalyze the reduction of CO₂ to HCOOH using water as the proton source with 97% yield with no detectable H₂ or CO. The iron porphyrinoid can activate CO₂ in its Fe(I) state resulting in very low overpotential for CO₂ reduction in contrast to all reported iron porphyrins, which can reduce CO₂ in their Fe(0) state. Intermediates involved in CO₂ reduction, Fe(III)–COOH and a Fe(II)–COOH, are identified with in situ FTIR-SEC and subsequently chemically generated and characterized using FTIR, resonance Raman, and Mössbauer spectroscopy. The mechanism of the reaction helps elucidate a key role played by a closely placed proton transfer residue in aiding CO₂ binding to Fe(I), stabilizing the intermediates, and determining the fate of a rate-determining Fe(II)–COOH intermediate.
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