Characterization and Properties of Non-Heme Iron Peroxo Complexes
Characterization and Properties of Non-Heme Iron Peroxo Complexes
复制标题
非血红素过氧化铁络合物的表征和性能
DOI：
10.1007/3-540-46592-8_6
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
A. Simaan
中科院分区：
文献类型：
--
作者：
J. Girerd;F. Banse;A. Simaan
铁-过氧Fe（III）O2和氢过氧Fe（III）OOH体系是许多单铁生物分子中初始Fe（II）-双氧加合物和催化位点的“活化”形式之间的重要中间体。在二铁酶中，相同的过氧化物水平对应于桥连的过氧Fe（III）-O-O-Fe（III）中间体。本文综述了非血红素化学体系中这类中间体的制备和光谱表征，并引用天然体系的性质作为参考。虽然没有一个被结晶，但Fe（III）OOH体系似乎很可能存在氢过氧基团的η 1 -配位模式。这些Fe（III）OOH单元在UV-vis、共振拉曼和质谱中给出了清晰的特征。通过EPR发现，在Fe（III）OOH中，Fe（III）是低自旋的（S = 1/2），我们在这里提出了EPR g张量特征的一个简单合理化。目前已知的Fe（III）（η1-OOH）的电子性质指向一个强的Fe-O键和一个弱的O-O键，这与反应性方案完全一致，该方案暗示O-O键的断裂在形式上导致Fe（V）O单元。烷基过氧体系也包括在这次审查。Fe（III）-过氧体系Fe（III）O2已制备和描述。它们含有高自旋Fe（III），并且被鉴定的似乎是η 2型。与Fe（III）OOH体系相比，Fe-O键较弱，O-O键较强。这些Fe（III）O2单元在催化中的含义尚不清楚。“互补”体系，如Fe（III）（η 1-OO）或Fe（III）（η 2-OOH）已在出版物中提及，但未通过光谱鉴定。这些系统当然值得积极研究。
Iron-peroxo Fe(III)O2 and hydroperoxo Fe(III)OOH systems are important intermediates between the initial Fe(II)-dioxygen adduct and the “activated” form of the catalytic site in many mono-iron biomolecules. To the same peroxidic level correspond, in diiron enzymes, bridged peroxo Fe(III)-O-O-Fe(III) intermediates. This review is concerned with the preparation and spectroscopic characterization of such intermediates in non-heme chemical systems, the properties of the natural systems being quoted as references. Although none have been crystallized, it seems very likely that Fe(III)OOH systems present a η 1 - coordination mode for the hydroperoxo group. These Fe(III)OOH units have given clear signatures in UV-vis, resonance Raman and mass spectrometry. By EPR it was found that in Fe(III)OOH, the Fe(III) is low-spin (S = 1/2) and we propose here a simple rationalization of the characteristics of the EPR g-tensor. The electronic properties of the Fe(III)(η1-OOH) known so far, point toward a strong Fe-O bond and a weak O-O bond, in total agreement with the reactivity scheme implying a cleavage of the O-O bond to lead formally to a Fe(V)O unit. Alkylperoxo systems are also included in this review. Fe(III)-peroxo systems Fe(III)O2 have been prepared and described. They contain high-spin Fe(III) and those identified seem to be of the η 2 type. The Fe-O bond is weaker and the O-O one is stronger than in the Fe(III)OOH systems. The implication of these Fe(III)O2 units in catalysis is unclear. “Complementary” systems, such as Fe(III)(η 1-OO) or Fe(III)(η 2-OOH) have been evoked in publications but not identified spectroscopically. These systems certainly deserve to be actively looked for.
影响因子：
2.9
作者：
Broadwater, JA;Ai, JY;Fox, BG
通讯作者：
Fox, BG
影响因子：
2.9
作者：
Lee, SY;Lipscomb, JD
通讯作者：
Lipscomb, JD