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非血红素铁-氮杂环卡宾/铁-氧物种介导的分子内邻位胺化/羟基化反应的机理研究：σ通道与π通道

Mechanistic insights into intramolecular ortho-amination/hydroxylation by nonheme Fe[double bond, length as m-dash]NTs/Fe[double bond, length as m-dash]O species: the σ vs. the π channels.

作者信息

Pandey Bhawana, Jaccob Madhavan, Rajaraman Gopalan

机构信息

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra 400076, India.

出版信息

Chem Commun (Camb). 2017 Mar 14;53(22):3193-3196. doi: 10.1039/c6cc08761b.

DOI:10.1039/c6cc08761b
PMID:28220156
Abstract

Comparative oxidative abilities of nonheme Fe[double bond, length as m-dash]NTs and Fe[double bond, length as m-dash]O species using DFT has been explored. Our calculations reveal that the Fe[double bond, length as m-dash]NTs is found to be a stronger oxidant in two electron transfer reactions and react exclusively via π channels while the Fe[double bond, length as m-dash]O species is found to be a stronger oxidant when the σ-pathway is activated such as in HAT reactions.

摘要

利用密度泛函理论（DFT）研究了非血红素Fe═NTs和Fe═O物种的相对氧化能力。我们的计算表明，在双电子转移反应中，Fe═NTs是更强的氧化剂，且仅通过π通道反应；而当σ途径被激活时，如在氢原子转移（HAT）反应中，Fe═O物种是更强的氧化剂。

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