Reactivity of [Fe(SAr)_4]^<n-> (n=1 or 2) : Synthetic Model Complexes for Iron-Sulfur Protein, Rubredoxin

概要

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Synthetic model complexes, (Et_4N)[Fe(S-p-C_6H_4X)_4], for the oxidized form of rubredoxin (Rd) were prepared in CH_3CN solution by the ligand-substitution of (Et_4N)[Fe(S_2-o-xyl)_2] with diaryl disulfides in The presence of o-xylene-α, α'-dithiol. The complex (X=H) exhibited an intense electron spin resonance (ESR) signal at g=4.3,due to the Fe(III) metal with the highly symmetrical ligand. The complex in the reduced state, [Fe(S-p-tol)_4]^<2->, was found to reduce tert-butyl hydroperoxide to tert-butyl alcohol stoichiometrically. Rubredoxin is believed to act as an electron carrier in the reduction of alkyl hydroperoxides to the corresponding alcohols in the ω-hydroxylation of alkanes in Pseudomonas olevorans. Thus, the reaction could be considered as biomimetic reduction by a rubredoxin model complex. The reaction mechanisms are discussed in connection with the characterization of the novel complexes.
公益社団法人日本薬学会の論文
1988-02-25