A high-valent manganese(IV)-hydroxo porphyrin π-cation radical complex, [Mn(IV)(OH)(Porp+•)(X)]+, was synthesized and characterized spectroscopically. The Mn porphyrin intermediate was highly reactive in alkane hydroxylation and oxygen atom transfer reactions. More importantly, the Mn porphyrin intermediate reacted with water at a fast rate, resulting in the dioxygen evolution. To the best of our knowledge, we report the first manganese Cpd I model compound bearing a porphyrin π-cation radical ligand with a high reactivity in oxidation reactions, including water oxidation.
Bibliographical noteFunding Information:
This work was supported by the NRF of Korea (NRF-2021R1A3B1076539 to W.N., NRF-2020R1I1A1A01074630 to Y.-M.L., and NRF-2021R1A2C1012851 to K.-B.C). This research was also supported by NSF CHE-2004147 to Y.P. The use of the Advanced Photon Source, an Office of Science User Facility operated by the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02- 06CH11357. The PNC/XSD (Sector 20) facilities at the Advanced Photon Source and research at these facilities were supported by the U.S. Department of Energy, Basic Energy Science, and the Canadian Light Source.
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