Reactivity of hydroperoxide bound to a mononuclear non-heme iron site
Reactivity of hydroperoxide bound to a mononuclear non-heme iron site
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DOI：
10.1021/ic001058h
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发表时间：
2002-02-25
影响因子：
4.6
通讯作者：
Masuda, H
中科院分区：
文献类型：
--
作者：
Wada, A;Ogo, S;Masuda, H
本文首次报道了单核氢过氧铁（Ⅲ）配合物[Fe（H（2）bppa）（OOH）]（2+）（2）的分离和光谱表征，以及由其分解产生的单核铁氧中间体对底物的化学计量氧化。[Fe（H（2）bppa）（HCOO）]（ClO_4）（2）与H_2O_2在丙酮中于-50 ℃反应得到的紫色物种2具有特征紫外-可见光谱（λ（max）= 568 nm，λ = 1200 M-1 cm（-1）），ESR（g = 7.54、5.78和4.25，S = 5/2）和ESI质谱（m/z 288.5，对应于离子[Fe（bppa）（OOH）]（2+）），其揭示2是以末端方式与氢过氧化物的高自旋单核铁（III）络合物。2在d（6）-丙酮中的共振拉曼光谱显示在621和830 cm（-1）处的两个强带，当与O-18标记的H2 O2反应时，这两个强带分别移动到599和813 cm（-1）。分离的（bppa）Fe-III-OOH（2）与各种底物的反应（单周转氧化）表明，由2分解产生的铁-氧代中间体是亲核物质，其公式为[（H2 bppa）Fe-III-O*]。
The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H(2)bppa)(OOH)](2+) (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H(2)bppa) (HCOO)] (CIO4)(2) with H2O2 in acetone at -50 degreesC gave characteristic UV-vis (lambda(max) = 568 nm, epsilon = 1200 M-1 cm(-1)), ESR (g = 7.54, 5.78, and 4.25, S = 5/2), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)](2+)), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d(6)-acetone revealed two intense bands at 621 and 830 cm(-1), which shifted to 599 and 813 cm(-1), respectively, when reacted with O-18-labeled H2O2. Reactions of the isolated (bppa)Fe-III-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H2bppa)Fe-III-O*].