期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 19, 页码 5086-5098出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201806430
关键词
biomimetic models; density functional calculations; iron-oxo; kinetics; steric effect
资金
- Department of Science and Technology (SERB), India [EMR/2014/000279]
- British Council [DST/INT/UK/P-151/2017]
- Department of Biotechnology, New Delhi [BT/PR14510/BID/07/334/2010]
Iron is an essential element in nonheme enzymes that plays a crucial role in many vital oxidative transformations and metabolic reactions in the human body. Many of those reactions are regio- and stereospecific and it is believed that the selectivity is guided by second-coordination sphere effects in the protein. Here, results are shown of a few engineered biomimetic ligand frameworks based on the N4Py (N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) scaffold and the second-coordination sphere effects are studied. For the first time, selective substitutions in the ligand framework have been shown to tune the catalytic properties of the iron(IV)-oxo complexes by regulating the steric and electronic factors. In particular, a better positioning of the oxidant and substrate in the rate-determining transition state lowers the reaction barriers. Therefore, an optimum balance between steric and electronic factors mediates the ideal positioning of oxidant and substrate in the rate-determining transition state that affects the reactivity of high-valent reaction intermediates.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据