Journal
ORGANOMETALLICS
Volume 38, Issue 6, Pages 1219-1223Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.8b00334
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Funding
- NSF Graduate Research Fellowship Program
- Solar Photochemistry Program of the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-SC0017619]
- U.S. Department of Energy (DOE) [DE-SC0017619] Funding Source: U.S. Department of Energy (DOE)
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Iron hangman porphyrins with phenol, guanidinium, and sulfonic acid proton donor groups placed above the Fe porphyrin platform reduce CO2 to CO with Faradaic efficiencies >93%. Computations show that the activation of CO2 at the Fe center is enhanced by the hanging group. Intramolecular hydrogen bonding from the phenol and guanidinium groups results in a 2.1-6.6 kcal/mol stabilization of CO2 within the hangman pocket; the hanging sulfonate group is deprotonated, thus resulting in destabilization of the CO2 adduct due to unfavorable electrostatic interactions. Electrochemical studies show that Fe hangman porphyrins exhibit canonical S-curve character; together with computation results, the apparent rate constant for CO2 reduction is found to be governed by CO2 binding within the hangman cleft.
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