title: Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand.
abstract: The addition of an organic acid to the manganese(V)-oxo corrole complex (tpfc)Mn(V)(O) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole) induces valence tautomerization resulting in the formation of (tpfc(+•))Mn(IV)(OH) in acetonitrile at 298 K. The corrole radical cation manganese(IV) hydroxo complex has been fully characterized by EPR, (1)H NMR, and UV-vis spectroscopy. The reactivity of the valence tautomer (tpfc(+•))Mn(IV)(OH) is compared to that of (tpfc)Mn(V)(O) in three reaction types: hydrogen atom transfer (HAT), electron transfer (ET), and oxygen atom transfer (OAT). (tpfc(+•))Mn(IV)(OH) shows a dramatic 5 orders of magnitude enhancement in the rate of ET but surprisingly does not undergo OAT with PhSMe. The high-valent (tpfc)Mn(V)(O) complex is moderately more reactive toward HAT with substituted phenol and shows superior activity in OAT.
authors.affiliation: Brown Laboratory, Department of Chemistry, Negishi-Brown Institute for Catalysis (NBIC), Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907, United States.
authors.forename: Curt J
authors.initials: CJ
authors.lastname: Bougher
authors.affiliation: Brown Laboratory, Department of Chemistry, Negishi-Brown Institute for Catalysis (NBIC), Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907, United States.
authors.forename: Shuo
authors.initials: S
authors.lastname: Liu
authors.affiliation: Brown Laboratory, Department of Chemistry, Negishi-Brown Institute for Catalysis (NBIC), Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907, United States.
authors.forename: Scott D
authors.initials: SD
authors.lastname: Hicks
authors.affiliation: Brown Laboratory, Department of Chemistry, Negishi-Brown Institute for Catalysis (NBIC), Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907, United States.|School of Chemical Engineering, Purdue University , Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette, Indiana 47907, United States.
authors.forename: Mahdi M
authors.initials: MM
authors.lastname: Abu-Omar