A synthetic precedent for the [FeIV2(mu-O)2] diamond core proposed for methane monooxygenase intermediate Q.

ABSTRACT: Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [Fe(IV)(2)(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 [Fe(III)Fe(IV)(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 Mössbauer spectrum of 2b exhibits a quadrupole doublet with delta = -0.04(1) mm.s(-1) and DeltaE(Q) = 2.09(2) mm.s(-1), parameters typical of an iron(IV) center. The Mössbauer patt

SUBMITTER: Xue G 

PROVIDER: S-EPMC2409154 | biostudies-literature | 2007 Dec

REPOSITORIES: biostudies-literature