Li Chunsen, Wu Wei, Kumar Devesh, Shaik Sason
State Key Laboratory of Physical Chemistry of Solid Surfaces, Center for Theoretical Chemistry, and Department of Chemistry, Xiamen University, PR China.
J Am Chem Soc. 2006 Jan 18;128(2):394-5. doi: 10.1021/ja055987p.
This paper presents DFT calculations of C-H hydroxylation of N,N-dimethylaniline by Compound I (Cpd I) of cytochrome P450. The reaction involves two processes nascent from the two spin states of Cpd I, the low-spin (LS) and high-spin (HS) states. The calculations demonstrate that the kinetic isotope effects (KIEs) of the two processes are very different, and only KIELS fits the experimental datum. As such, KIE can be a sensitive probe of spin state reactivity.
本文介绍了细胞色素P450的化合物I（Cpd I）对N，N-二甲基苯胺进行C-H羟基化反应的密度泛函理论（DFT）计算。该反应涉及从Cpd I的两种自旋态即低自旋（LS）态和高自旋（HS）态产生的两个过程。计算表明，这两个过程的动力学同位素效应（KIEs）有很大差异，只有低自旋态的KIE（KIELS）符合实验数据。因此，KIE可以作为自旋态反应活性的灵敏探针。
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