Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand
Journal of the American Chemical Society
by Curt J. Bougher, Shuo Liu, Scott D. Hicks and Mahdi M. Abu-Omar
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http://pubs.acs.org/doi/pdf/10.1021/jacs.5b09759
The addition of an organic acid to the manganese(V)-oxo corrole complex (tpfc)MnV(O) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole) induces valence tautomerization resulting in the formation of (tpfc+•)MnIV(OH) in acetonitrile at 298 K. The corrole radical cation manganese(IV) hydroxo complex has been fully characterized by EPR, 1H NMR, and UV–vis spectroscopy. The reactivity of the valence tautomer (tpfc+•)MnIV(OH) is compared to that of (tpfc)MnV(O) in three reaction types: hydrogen atom transfer (HAT), electron transfer (ET), and oxygen atom transfer (OAT). (tpfc+•)MnIV(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)MnV(O) complex is moderately more reactive toward HAT with substituted phenol and shows superior activity in OAT.
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http://pubs.acs.org/doi/pdf/10.1021/jacs.5b09759
The addition of an organic acid to the manganese(V)-oxo corrole complex (tpfc)MnV(O) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole) induces valence tautomerization resulting in the formation of (tpfc+•)MnIV(OH) in acetonitrile at 298 K. The corrole radical cation manganese(IV) hydroxo complex has been fully characterized by EPR, 1H NMR, and UV–vis spectroscopy. The reactivity of the valence tautomer (tpfc+•)MnIV(OH) is compared to that of (tpfc)MnV(O) in three reaction types: hydrogen atom transfer (HAT), electron transfer (ET), and oxygen atom transfer (OAT). (tpfc+•)MnIV(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)MnV(O) complex is moderately more reactive toward HAT with substituted phenol and shows superior activity in OAT.
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