Mechanism of Catalytic O2 Reduction by Iron Tetraphenylporphyrin

Pegis, Michael L.; Martin, Daniel J.; Wise, Catherine F.; Brezny, Anna C.; Johnson, Samantha JI; Johnson, Lewis E.; Kumar, Neeraj; Raugei, Simone; Mayer, James M.

doi:10.1021/jacs.9b02640

Mechanism of Catalytic O2 Reduction by Iron Tetraphenylporphyrin

Journal Article · Wed May 22 04:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b02640· OSTI ID:1543301

Pegis, Michael L. ^[1]; Martin, Daniel J. ^[2]; Wise, Catherine F. ^[2]; Brezny, Anna C. ^[2]; Johnson, Samantha JI ^[3]; Johnson, Lewis E. ^[4]; ^[3]; Raugei, Simone ^[3]; Mayer, James M. ^[2]

YALE UNIVERSITY
Yale University
BATTELLE (PACIFIC NW LAB)
UNIVERSITY OF WASHINGTON (MAIN CAMPUS)

The catalytic reduction of O2 to H2O is important for energy transduction in both synthetic and natural systems. Herein, we report a kinetic study of O2 reduction catalyzed by iron tetraphenylporphyrin in N,N-dimethylformamide using decamethylferrocene as a soluble reductant and para-toluenesulfonic acid (pTsOH) as the proton source. Reduction of the ferric porphyrin, [FeIII(TPP)]+ , forms the ferrous porphyrin, FeII(TPP), which binds O2 reversibly to form the ferric-superoxide porphyrin complex, FeIII(TPP)(O2 •?). The temperature dependence of both the electron transfer and O2 binding equilibrium constants have been determined. Kinetic studies over a range of concentrations and temperatures show that the catalyst resting state changes during the course of each catalytic run, necessitating the use of global kinetic modeling to extract rate constants and kinetic barriers. The rate-determining step in oxygen reduction is protonation of FeIII(TPP)(O2•?) by pTsOH, which proceeds with a substantial kinetic barrier. Computational studies indicate that this barrier for proton transfer arises from an unfavorable pre-association of the proton donor with the superoxide adduct and a transition state that requires significant desolvation of the proton donor. Together, these results are the first example of oxygen reduction by iron tetraphenylporphyrin where the pre-equilibria between ferric, ferrous, and ferric-superoxide intermediates have been quantified under catalytic conditions. This work gives a generalizable model for the mechanism of iron porphyrin-catalyzed ORR and provides an unusually complete mechanistic study of an ORR reaction. More broadly, this study also highlights the kinetic challenges for proton transfer to catalytic intermediates in organic media.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1543301

Report Number(s):: PNNL-SA-141930

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 141

Country of Publication:: United States

Language:: English

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