Second sphere control of CO2 reduction selectivity by iron porphyrins: The role of spin state

Iron porphyrins are reported to reduce CO2 selectively to CO. Hydrogen bonding interactions are reported to facilitate this 2e−/2H+ reduction process. A series of iron porphyrins are reported here where hydrogen bonding distal super structure is introduced systematically. The results show that the selectivity for 2e−/2H+ CO2 reduction changes dramatically from CO to HCOOH as hydrogen bonding interactions are introduced. The resonance Raman data of the Fe(II)-COOH intermediate, trapped at −80oC, show that the spin state of this species changes from low spin to high spin as hydrogen bonding is introduced. The spin state of the Fe(II)-COOH intermediate seems to determine the selectivity of 2e−/2H+ CO2 reduction in iron porphyrins. © 2024