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Stabilization of Higher-Valent States of Iron Porphyrin by Hydroxide and Methoxide Ligands: Electrochemical Generation of Iron (IV)-Oxo Porphyrins

William A. Lee, Thomas S. Calderwood and Thomas C. Bruice
Proceedings of the National Academy of Sciences of the United States of America
Vol. 82, No. 13 (Jul. 1, 1985), pp. 4301-4305
Stable URL: http://www.jstor.org/stable/25791
Page Count: 5
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Since scans are not currently available to screen readers, please contact JSTOR User Support for access. We'll provide a PDF copy for your screen reader.
Stabilization of Higher-Valent States of Iron Porphyrin by Hydroxide and Methoxide Ligands: Electrochemical Generation of Iron (IV)-Oxo Porphyrins
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Abstract

An electrochemical study of hydroxide- and methoxide-ligated iron(III) tetraphenylporphyrins possessing ortho-phenyl substituents that block μ -oxo dimer formation has been carried out. Ligation by these strongly basic oxyanions promotes the formation of iron(IV)-oxo porphyrins upon one-electron oxidation. Further one-electron oxidation of the latter provides the iron(IV)-oxo porphyrin π -cation radical. These results are discussed in terms of chemical model studies and the enzymatic intermediate compounds I and II of the peroxidases.

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