Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid

Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid

Addition of the Lewis acid Zn2+ to (TBP8Cz)MnV(O) induces valence tautomerization, resulting in the formation of [(TBP8Cz+•)MnIV(O)–Zn2+]. This new species was characterized by UV–vis, EPR, the Evans method, and 1H NMR and supported by DFT calculations. Removal of Zn2+ quantitatively restores the st...

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Veröffentlicht in:Journal of the American Chemical Society 2012-06, Vol.134 (25), p.10397-10400
Hauptverfasser: Leeladee, Pannee, Baglia, Regina A, Prokop, Katharine A, Latifi, Reza, de Visser, Sam P, Goldberg, David P
Format: Artikel
Sprache:eng
Schlagworte:
Lewis Acids - chemistry
Magnetic Resonance Spectroscopy
Manganese - chemistry
Metalloporphyrins - chemistry
Molecular Structure
Quantum Theory
Stereoisomerism
Zinc - chemistry
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Zusammenfassung:Addition of the Lewis acid Zn2+ to (TBP8Cz)MnV(O) induces valence tautomerization, resulting in the formation of [(TBP8Cz+•)MnIV(O)–Zn2+]. This new species was characterized by UV–vis, EPR, the Evans method, and 1H NMR and supported by DFT calculations. Removal of Zn2+ quantitatively restores the starting material. Electron-transfer and hydrogen-atom-transfer reactions are strongly influenced by the presence of Zn2+.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja304609n