Characterization of a high-spin non-heme Fe(III)-OOH intermediate and its quantitative conversion to an Fe(IV)═O complex.

Characterization of a high-spin non-heme Fe(III)-OOH intermediate and its quantitative conversion to an Fe(IV)═O complex.
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DOI:
10.1021/ja111742z
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发表时间:
2011-05-18
影响因子:
15
通讯作者:
Que, Lawrence, Jr.
Que, Lawrence, Jr.
中科院分区:
化学1区
文献类型:
--
作者:
Li, Feifei;Meier, Katlyn K.;Cranswick, Matthew A.;Chakrabarti, Mrinmoy;Van Heuvelen, Katherine M.;Muenck, Eckard;Que, Lawrence, Jr.

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我们已经产生了一个高自旋FeIII-OOH配合物支持的四甲基cyclam通过质子化的共轭碱,并通过各种光谱方法进行了详细的表征。这种FeIII-OOH物质通过O-O键断裂定量转化为FeIV=O络合物,这代表了这种转化的第一个实例。这种转化由两个因素促进:抑制Fe-O键裂解的强FeIII-OOH键和促进O-O键裂解的质子的添加。该实施例提供了如何促进非血红素铁酶的高自旋铁(III)-过氧中间体的O-O键断裂的合成先例。
We have generated a high-spin FeIII–OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail by various spectroscopic methods. This FeIII–OOH species converts quantitatively to an FeIV=O complex via O–O bond cleavage, which represents the first example of such a conversion. This conversion is promoted by two factors: the strong FeIII–OOH bond that inhibits Fe–O bond lysis and the addition of protons that facilitate O–O bond cleavage. This example provides a synthetic precedent for how O–O bond cleavage of high-spin iron(III)-peroxo intermediates of nonheme iron enzymes may be promoted.
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