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1H-ENDOR 证据表明氢键相互作用调节非血红素 Fe(IV)═O 单元的反应性。

1H-ENDOR evidence for a hydrogen-bonding interaction that modulates the reactivity of a nonheme Fe(IV)═O unit.

机构信息

Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA.

出版信息

Inorg Chem. 2012 Oct 1;51(19):10080-2. doi: 10.1021/ic3015783. Epub 2012 Sep 17.

DOI:10.1021/ic3015783
PMID:22984805
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3482979/
Abstract

We report that a novel use of 35 GHz (1)H-ENDOR spectroscopy establishes the presence in 1 of an Fe(IV)═O···H-O-Fe(III) hydrogen bond predicted by density functional theory computations to generate a six-membered-ring core for 1. The hydrogen bond rationalizes the difference in the C-H bond cleavage reactivity between 1 and 4(OCH(3)) (where a CH(3)O group has replaced the HO on the Fe(III) site). This result substantiates the seemingly paradoxical conclusion that the nonheme Fe(IV)═O unit of 1 not only has the electrophilic character required for H-atom abstraction but also retains sufficient nucleophilic character to accept a hydrogen bond from the Fe(III)-OH unit.

摘要

我们报告了一种新颖的 35GHz（1）H-ENDOR 光谱技术的应用，该技术证实了 1 中存在 Fe(IV)═O···H-O-Fe(III)氢键，这是通过密度泛函理论计算预测的，用于生成 1 的六元环核心。氢键解释了 1 和 4（OCH(3)）（其中一个 CH(3)O 基团取代了 Fe(III)位上的 HO）之间 C-H 键断裂反应性的差异。这一结果证实了一个看似矛盾的结论，即 1 的非血红素 Fe(IV)═O 单元不仅具有所需的亲电性，用于 H 原子的攫取，而且还保留了足够的亲核性，能够接受来自 Fe(III)-OH 单元的氢键。

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