NDLI: A synthetic precedent for the [FeIV 2(μ-O)2] diamond core proposed for methane monooxygenase intermediate Q

Content Provider	PubMed Central
Author	Xue, Genqiang Wang, Dong Hont, Raymond De Fiedler, Adam T. Shan, Xiaopeng Eckard, Münck Que, Lawrence
Copyright Year	2007
Abstract	Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [FeIV 2(μ-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°C on a valence-delocalized [FeIIIFeIV(μ-O)2(Lb)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 λmax at 485 nm (9,800 M−1·cm−1) and 875 nm (2,200 M−1·cm−1). The 4.2 K Mössbauer spectrum of 2b exhibits a quadrupole doublet with δ = −0.04(1) mm·s−1 and ΔE Q = 2.09(2) mm·s−1, parameters typical of an iron(IV) center. The Mössbauer 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 [Fe2(μ-O)2] core at 674 cm−1, downshifting 30 cm−1 upon 18O labeling. Extended x-ray absorption fine structure (EXAFS) analysis shows two O/N scatterers at 1.78 Å and an Fe scatterer at 2.73 Å. Based on the accumulated spectroscopic evidence, 2b thus can be formulated as [FeIV 2(μ-O)2(Lb)2]4+, the first synthetic complex with an [FeIV 2(μ-O)2] core. A comparison of 2b and its mononuclear analog [FeIV(O)(Lb)(NCMe)]2+ (4b) reveals that 4b is 100-fold more reactive than 2b in oxidizing weak CH bonds. This surprising observation may shed further light on how intermediate Q carries out the hydroxylation of methane.
Related Links	http://dx.doi.org/10.1073/pnas.0708516105
Ending Page	20718
Page Count	6
Starting Page	20713
File Format	PDF
ISSN	00278424
e-ISSN	10916490
Journal	Proceedings of the National Academy of Sciences of the United States of America
Issue Number	52
Volume Number	104
Language	English
Publisher	National Academy of Sciences
Publisher Date	2007-12-26
Access Restriction	Open
Rights Holder	National Academy of Sciences
Subject Keyword	General Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Multidisciplinary

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