期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 109, 期 30, 页码 11933-11938出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1206457109
关键词
high-valent iron-oxo; bioinorganic chemistry
资金
- National Institutes of Health [GM33162, GM38767, EB001475, GM-093479, GM-079839]
- National Science Foundation [CHE1058248, CHE070073]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1058248] Funding Source: National Science Foundation
Oxoiron(V) species are postulated to be involved in the mechanisms of the arene cis-dihydroxylating Rieske dioxygenases and of bioinspired nonheme iron catalysts for alkane hydroxylation, olefin cis-dihydroxylation, and water oxidation. In an effort to obtain a synthetic oxoiron(V) complex, we report herein the one-electron oxidation of the S = 1 complex [Fe-IV(O)(TMC)(NCCH3)](2+) (1, where TMC is tetramethylcyclam) by treatment with tert -butyl hydroperoxide and strong base in acetonitrile to generate a meta-stable S = 1/2 complex 2 at -44 degrees C, which has been characterized by UV-visible, resonance Raman, Mossbauer, and EPR methods. The defining spectroscopic characteristic of 2 is the unusual x/y anisotropy observed for the Fe-57 and O-17 A tensors associated with the high-valent Fe=O unit and for the N-14 A tensor of a ligand derived from acetonitrile. As shown by detailed density functional theory (DFT) calculations, the unusual x/y anisotropy observed can only arise from an iron center with substantially different spin populations in the d(xz) and d(yz) orbitals, which cannot correspond to an Fe-IV=O unit but is fully consistent with an S = 1/2 Fe-V center, like that found for [Fe-V(O)(TAML)](-) (where TAML is tetraamido macrocyclic ligand), the only well-characterized oxoiron(V) complex reported. Mass spectral analysis shows that the generation of 2 entails the addition of an oxygen atom to 1 and the loss of one positive charge. Taken together, the spectroscopic data and DFT calculations support the formulation of 2 as an iron(V) complex having axial oxo and acetylimido ligands, namely [Fe-V(O)(TMC)(NC(O)(CH3)](+).
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