高核价双铁配合物与酶中间物的核共振振动光谱和计算研究。
Nuclear resonance vibrational spectroscopic and computational study of high-valent diiron complexes relevant to enzyme intermediates.
机构信息
Department of Chemistry, Stanford University, Stanford, CA 94305, USA.
出版信息
Proc Natl Acad Sci U S A. 2013 Apr 16;110(16):6275-80. doi: 10.1073/pnas.1304238110. Epub 2013 Apr 1.
Abstract
High-valent intermediates of binuclear nonheme iron enzymes are structurally unknown despite their importance for understanding enzyme reactivity. Nuclear resonance vibrational spectroscopy combined with density functional theory calculations has been applied to structurally well-characterized high-valent mono- and di-oxo bridged binuclear Fe model complexes. Low-frequency vibrational modes of these high-valent diiron complexes involving Fe motion have been observed and assigned. These are independent of Fe oxidation state and show a strong dependence on spin state. It is important to note that they are sensitive to the nature of the Fe2 core bridges and provide the basis for interpreting parallel nuclear resonance vibrational spectroscopy data on the high-valent oxo intermediates in the binuclear nonheme iron enzymes.
摘要
双核非血红素铁酶的高价中间体的结构尽管对于理解酶反应性很重要，但仍然未知。核共振振动光谱结合密度泛函理论计算已应用于结构特征良好的高价单氧和双氧桥联双核 Fe 模型配合物。这些高价二铁配合物中涉及 Fe 运动的低频振动模式已经被观察到并被分配。这些模式与 Fe 氧化态无关，但与自旋态有很强的依赖性。值得注意的是，它们对 Fe2 核心桥的性质敏感，并为解释双核非血红素铁酶中高价氧中间体的核共振振动光谱数据提供了基础。
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