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.
中科院分区:
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.
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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