期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 104, 期 52, 页码 20713-20718出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0708516105
关键词
diiron(IV); iron-oxo; nonheme; oxygen activation; electrochemistry
资金
- NIBIB NIH HHS [EB-001475, R01 EB001475] Funding Source: Medline
- NIGMS NIH HHS [R01 GM038767, GM38767, F32 GM079839] Funding Source: Medline
- PHS HHS [FGM079839] Funding Source: Medline
Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [Fe-2(IV)(mu-O)(2)] diamond core. In an effort to obtain a synthetic precedent for such a core, bulk electrolysis at 900 mV (versus Fc(+/0)) has been performed in MeCN at -40 degrees C on a valence-delocalized [(FeFeIV)-Fe-III(mu-O)(2)(L-b)(2)](3+) complex (1b) (E-1/2 = 760 mV versus Fc(+/0)). Oxidation of 1b results in the near-quantitative formation of a deep red complex, designated 2b, that exhibits a visible spectrum with lambda(max) at 485 nm (9,800 M-1.cm(-1)) and 875 nm (2,200 M-1.cm(-1)). The 4.2 K Mossbauer spectrum of 2b exhibits a quadrupole doublet with delta = -0.04(1) mm.s(-1) and Delta E-Q = 2.09(2) mm.s(-1), parameters typical of an iron(IV) center. The Mossbauer patterns observed in strong applied fields show that 2b is an antiferromagnetically coupled diiron(IV) center. Resonance Raman studies reveal the diagnostic vibration mode of the [Fe-2(mu-O)(2)] core at 674 cm(-1), downshifting 30 cm(-1) upon O-18 labeling. Extended x-ray absorption fine structure (EXAFS) analysis shows two O/N scatterers at 1.78 angstrom and an Fe scatterer at 2.73 angstrom. Based on the accumulated spectroscopic evidence, 2b thus can be formulated as [Fe-2(IV)(mu-O)(2)(L-b)(2)](4+), the first synthetic complex with an [Fe-IV(mu-O)(2)] core. A comparison of 2b and its mononuclear analog [Fe-IV(O)(L-b)(NCMe)](2+) (4b) reveals that 4b is 100-fold more reactive than 2b in oxidizing weak C-H bonds. This surprising observation may shed further light on how intermediate Q carries out the hydroxylation of methane.
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