N–O Bond Homolysis of an Iron(II) TEMPO Complex Yields an Iron(III) Oxo Intermediate

The reaction of TEMPO with the iron(I) synthon PhB(MesIm)3Fe(COE) leads to formation of the κ1-TEMPO complex PhB(MesIm)3Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2012-04, Vol.134 (15), p.6516-6519
Main Authors: Smith, Jeremy M., Mayberry, Derick E., Margarit, Charles G., Sutter, Jörg, Wang, Haobin, Meyer, Karsten, Bontchev, Ranko P.
Format: Article
Language:English
Subjects:
Cyclic N-Oxides - chemistry
Iron - chemistry
Oxygen - chemistry
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Summary:The reaction of TEMPO with the iron(I) synthon PhB(MesIm)3Fe(COE) leads to formation of the κ1-TEMPO complex PhB(MesIm)3Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis of the complex results in N–O bond homolysis, leading to the formation of an iron(III) oxo intermediate. The oxo intermediate is active in oxygen atom transfer reactions and can be trapped by the triphenylmethyl radical to give the iron(II) alkoxo complex PhB(MesIm)3Fe(OCPh3).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja211882e