Note to users. If you're seeing this message, it means that your browser cannot find this page's style/presentation instructions -- or possibly that you are using a browser that does not support current Web standards. Find out more about why this message is appearing, and what you can do to make your experience of our site the best it can be.
O2 Activation by Nonheme Iron Complexes: A Monomeric Fe(III)-Oxo Complex Derived From O2
Cora E. MacBeth,1Adina P. Golombek,3Victor G. Young Jr.,4Cheng Yang,1Krzysztof Kuczera,12Michael P. Hendrich,3A. S. Borovik1*
Iron species with terminal oxo ligands are implicated as
key intermediates in several synthetic and biochemical catalyticcycles. However, there is a dearth of structural information regardingthese types of complexes because their instability has precludedisolation under ambient conditions. The isolation and structuralcharacterization of an iron(III) complex with a terminal oxo ligand,derived directly from dioxygen (O2), is reported. A
stable structureresulted from placing the oxoiron unit within a
synthetic cavitylined with hydrogen-bonding groups. The cavity creates
a microenvironmentaround the iron center that aids in regulating
O2 activation andstabilizing the oxoiron unit. These
cavities share propertieswith the active sites of metalloproteins,
where function is correlatedstrongly with site structure.
1 Department of Chemistry and
2 Department of Molecular Biosciences, University of
Kansas, Lawrence, KS 66045, USA.
3 Department of
Chemistry, Carnegie-Mellon University, Pittsburgh, PA 15213, USA.
4 Department of Chemistry, University of Minnesota,
Minneapolis, MN 55455, USA.
*
To whom correspondence should be addressed.
The editors suggest the following Related Resources on Science sites:
In Science Magazine
PERSPECTIVES
H. Holden Thorp (11 August 2000) Science289 (5481), 882.
[DOI: 10.1126/science.289.5481.882] |Summary »|Full Text »
THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
T315I-mutated Bcr-Abl in chronic myeloid leukemia and imatinib: insights from a computational study.
S. Pricl, M. Fermeglia, M. Ferrone, and E. Tamborini (2005)
Mol. Cancer Ther.
4, 1167-1174
|Abstract »|Full Text »|PDF »
A Late-Transition Metal Oxo Complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-.
T. M. Anderson, W. A. Neiwert, M. L. Kirk, P. M. B. Piccoli, A. J. Schultz, T. F. Koetzle, D. G. Musaev, K. Morokuma, R. Cao, and C. L. Hill (2004)
Science
306, 2074-2077
|Abstract »|Full Text »|PDF »
Bioinorganic Chemistry Special Feature: Synthetic modeling of zinc thiolates: Quantitative assessment of hydrogen bonding in modulating sulfur alkylation rates.
S.-J. Chiou, C. G. Riordan, and A. L. Rheingold (2003)
PNAS
100, 3695-3700
|Abstract »|Full Text »|PDF »
Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)&cjs0811;O Complex.
J.-U. Rohde, J.-H. In, M. H. Lim, W. W. Brennessel, M. R. Bukowski, A. Stubna, E. Munck, W. Nam, and L. Que Jr. (2003)
Science
299, 1037-1039
|Abstract »|Full Text »|PDF »