Experimental and Theoretical Evidence for Nonheme Iron(III) Alkylperoxo Species as Sluggish Oxidants in Oxygenation Reactions

The active oxidant that oxygenates organic substrates is an iron(IV) oxo intermediate, namely, [(tpa)FeIV(O)(CH3CN)]2+ (2), which is formed through OO bond homolysis, according to experimental and computational studies on the reactivity of nonheme iron(III) alkylperoxo complex [(tpa)FeIII(OOtBu)(CH3CN)]2+ (1), which was shown to be a sluggish electrophilic oxidant that is incapable of oxygenating organic substrates. tpa=tris(2-pyridylmethyl)amine. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z604219_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.