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Published Online December 21, 2006
Science DOI: 10.1126/science.1133417

Reports

Submitted on August 3, 2006
Accepted on December 12, 2006

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*, Emile L. Bominaar 1*, Eckard Münck 1*, Terrence J. Collins 1*

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.

* To whom correspondence should be addressed.
Lawrence Que Jr. , E-mail: que{at}chem.umn.edu
Emile L. Bominaar , E-mail: eb7g{at}andrew.cmu.edu
Eckard Münck , E-mail: emunck{at}cmu.edu
Terrence J. Collins , E-mail: tc1u{at}andrew.cmu.edu

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, reactivity studies, as well as density functional theory calculations, show that this long-lived (hours at -60°C) intermediate is an 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 newly characterized species is a likely reactive intermediate in these reactions.


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Science. ISSN 0036-8075 (print), 1095-9203 (online)