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Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)O Complex
Jan-Uwe Rohde,1*Jun-Hee In,12*Mi Hee Lim,12William W. Brennessel,1Michael R. Bukowski,1Audria Stubna,3Eckard Münck,3Wonwoo Nam,2Lawrence Que Jr.1
Following the heme paradigm, it is often proposed that dioxygen
activation by nonheme monoiron enzymes involves an iron(IV)=oxointermediate that is responsible for the substrate oxidation step.Such
a transient species has now been obtained from a syntheticcomplex with
a nonheme macrocyclic ligand and characterized spectroscopically.Its
high-resolution crystal structure reveals an iron-oxygen bondlength of
1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxounit can exist in a nonporphyrin ligand environment and lendingcredence to proposed mechanisms of nonheme iron catalysis.
1 Department of Chemistry and Center for Metals
in Biocatalysis, University of Minnesota, 207 Pleasant Street SE,
Minneapolis, MN 55455, USA.
2 Department of
Chemistry and Division of Molecular Life Sciences, Ewha Womans
University, Seoul 120-750, Korea.
3 Department of
Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.
*
These authors contributed equally to this work.
To whom correspondence should be addressed. E-mail:
emunck{at}cmu.edu (E.M.); wwnam{at}ewha.ac.kr (W.N.);
que{at}chem.umn.edu (L.Q.)
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PERSPECTIVES
Julie A. Kovacs (14 February 2003) Science299 (5609), 1024.
[DOI: 10.1126/science.1081792] |Summary »|Full Text »|PDF »
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Andreas Karlsson, Juanito V. Parales, Rebecca E. Parales, David T. Gibson, Hans Eklund, and S. Ramaswamy (14 February 2003) Science299 (5609), 1039.
[DOI: 10.1126/science.1078020] |Abstract »|Full Text »|PDF »|Supporting Online Material »
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O Complex
