Reaction of an iron(IV) nitrido complex with cyclohexadienes: Cycloaddition and hydrogen-atom abstraction

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题名:	Reaction of an iron(IV) nitrido complex with cyclohexadienes: Cycloaddition and hydrogen-atom abstraction
作者:	李韋宗;Lee, Wei-Tsung;Juarez, Ruth A;Scepaniak, Jeremiah J;Muñoz, Salvador B;Dickie, Diane A;Wang, Haobin;Smith, Jeremy M
贡献者:	理學院化學學系
关键词:	Cyclization;Cycloaddition;Cyclohexenes - chemistry;Diels-Alder reactions;Electronic structure;Formations;Hydrogen - chemistry;Iron Compounds - chemical synthesis;Iron Compounds - chemistry;Isomerization;Mathematical analysis;Molecular Conformation;Nitrogen Compounds - chemistry;Radicals;Reaction mechanisms
日期:	2014-08-18
上传时间:	2026-04-21 14:28:08 (UTC+8)
出版者:	American Chemical Society;United States: American Chemical Society
摘要:	摘要： The iron(IV) nitrido complex PhB(MesIm)3FeN reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η5-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product. 其他題名： Inorg. Chem 出版者： United States: American Chemical Society 出版日期： 2014-08-18 出處： Inorganic chemistry, 2014-08, Vol.53 (16), p.8425-8430 資源來源： ACS Publications (Open Access) 版權： Copyright © 2014 American Chemical Society 版權： Copyright © 2014 American Chemical Society 2014 American Chemical Society 識別號： ISSN: 0020-1669 識別號： ISSN: 1520-510X 識別號： EISSN: 1520-510X 識別號： DOI: 10.1021/ic5010006 識別號： PMID: 25068927
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