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Originally published in Science Express on 21 December 2006
Science 9 February 2007:
Vol. 315. no. 5813, pp. 835 - 838
DOI: 10.1126/science.1133417
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Reports

Chemical and Spectroscopic Evidence for an FeV-Oxo Complex

Filipe Tiago de Oliveira,1* Arani Chanda,1* Deboshri Banerjee,1 Xiaopeng Shan,2 Sujit Mondal,1 Lawrence Que, Jr.,2{dagger} Emile L. Bominaar,1{dagger} Eckard Münck,1{dagger} Terrence J. Collins1{dagger}

Iron(V)-oxo species have been proposed as key reactive intermediates in the catalysis of oxygen-activating enzymes and synthetic catalysts. Here, we report the synthesis of [Fe(TAML)(O)]– in nearly quantitative yield, where TAML is a macrocyclic tetraamide ligand. Mass spectrometry, Mössbauer, electron paramagnetic resonance, and x-ray absorption spectroscopies, as well as reactivity studies and density functional theory calculations show that this long-lived (hours at –60°C) intermediate is a spin S = 1/2 iron(V)-oxo complex. Iron-TAML systems have proven to be efficient catalysts in the decomposition of numerous pollutants by hydrogen peroxide, and the species we characterized is a likely reactive intermediate in these reactions.

1 Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.
2 Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA.

* These authors contributed equally to this work.

{dagger} To whom correspondence should be addressed. E-mail: que{at}chem.umn.edu (L.Q.); eb7g{at}andrew.cmu.edu (E.L.B.); emunck{at}cmu.edu (E.M.); tc1u{at}andrew.cmu.edu (T.J.C.)

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