Valence tautomerism in a high-valent manganese-oxo porphyrinoid complex induced by a Lewis acid.
Addition of the Lewis acid Zn(2+) to (TBP(8)Cz)Mn(V)(O) induces valence tautomerization, resulting in the formation of [(TBP(8)Cz(+•))Mn(IV)(O)-Zn(2+)]. This new species was characterized by UV-vis, EPR, the Evans method, and (1)H NMR and supported by DFT calculations. Removal of Zn(2+) quantitatively restores the starting material. Electron-transfer and hydrogen-atom-transfer reactions are strongly influenced by the presence of Zn(2+).
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
Pannee
P
Leeladee
Regina A
RA
Baglia
Katharine A
KA
Prokop
Reza
R
Latifi
Sam P
SP
de Visser
David P
DP
Goldberg
D058116:Lewis Acids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008345:Manganese / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D058116:Lewis Acids; D008665:Metalloporphyrins; D008345:Manganese; D015032:Zinc