Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)=O Complex
10.1126/science.299.5609.1037
Crossref journal-article
American Association for the Advancement of Science (AAAS)
Science (221)
Abstract

Following the heme paradigm, it is often proposed that dioxygen activation by nonheme monoiron enzymes involves an iron(IV)=oxo intermediate that is responsible for the substrate oxidation step. Such a transient species has now been obtained from a synthetic complex with a nonheme macrocyclic ligand and characterized spectroscopically. Its high-resolution crystal structure reveals an iron-oxygen bond length of 1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxo unit can exist in a nonporphyrin ligand environment and lending credence to proposed mechanisms of nonheme iron catalysis.

Bibliography

Rohde, J.-U., In, J.-H., Lim, M. H., Brennessel, W. W., Bukowski, M. R., Stubna, A., Münck, E., Nam, W., & Que, L. (2003). Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)=O Complex. Science, 299(5609), 1037–1039.

Authors 9
  1. Jan-Uwe Rohde (first)
  2. Jun-Hee In (additional)
  3. Mi Hee Lim (additional)
  4. William W. Brennessel (additional)
  5. Michael R. Bukowski (additional)
  6. Audria Stubna (additional)
  7. Eckard Münck (additional)
  8. Wonwoo Nam (additional)
  9. Lawrence Que (additional)
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  42. Supported by grants from NIH (GM-33162 and GM-38767 to L.Q. and GM-22701 to E.M.) and the Korea Science and Engineering Foundation (KOSEF) (R02-2002-000-00048-0 to W.N.) a postdoctoral fellowship from the Deutsche Forschungsgemeinschaft (J.-U.R.) and a graduate fellowship from NSF (A.S.). We also thank KOSEF and NSF for stimulating this international cooperative research effort.
Dates
Type When
Created 22 years, 6 months ago (Feb. 13, 2003, 5:06 p.m.)
Deposited 1 year, 7 months ago (Jan. 13, 2024, 10:49 a.m.)
Indexed 14 hours, 14 minutes ago (Aug. 28, 2025, 8:41 a.m.)
Issued 22 years, 6 months ago (Feb. 14, 2003)
Published 22 years, 6 months ago (Feb. 14, 2003)
Published Print 22 years, 6 months ago (Feb. 14, 2003)
Funders 0

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@article{Rohde_2003, title={Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)=O Complex}, volume={299}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.299.5609.1037}, DOI={10.1126/science.299.5609.1037}, number={5609}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Rohde, Jan-Uwe and In, Jun-Hee and Lim, Mi Hee and Brennessel, William W. and Bukowski, Michael R. and Stubna, Audria and Münck, Eckard and Nam, Wonwoo and Que, Lawrence}, year={2003}, month=feb, pages={1037–1039} }