铁催化惰性键活化的理论计算研究
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- 英文论文题名：Theoretical Studies on Inert Chemical Bond Activations by Iron Catalysts
- 论文作者：陈辉
- 英文论文作者：Hui Chen ; Beijing National Laboratory for Molecular Sciences(BNLMS) ; CAS Key Laboratory of Photochemistry ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：北京分子科学国家实验室,中国科学院化学研究所,光化学院重点实验室;
- 论文关键词：铁催化 ; 惰性键活化 ; 均相催化 ; 二态反应性
- 英文论文关键词：iron catalysis ; invert chemical bond activation ; homogeneous catalysis ; two-state reactivity
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O643.3
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：152k
- 原文格式：D
- 会议级别：全国
摘要
在均相过渡金属催化领域,铁催化惰性键活化反应一直是备受关注的前沿之一~([1])。铁作为第一过渡系的廉价过渡金属,相比于第二、三过渡系的贵金属,其体系常具有多个自旋态,以及复杂的开壳层电子结构,给通常的过渡金属体系理论计算处理带来了新的挑战。为理解铁催化惰性键活化的机理,最近,我们针对不同的铁催化体系,开展了系统性理论计算研究~([2-4]),研究涵盖了铁从+4价到零价的一系列氧化态。我们发现,不同氧化态的铁,在惰性键(如非活化C-H键)活化中,采取了完全不同的反应策略和机理。在活化C-H键时,零价铁倾向于使用氧化加成模式,而+2/+3价铁采用s-键复分解模式,+4高价铁则利用氢原子抓取模式。我们的研究在国际上首次提出了低价铁活化惰性C-H键的二态反应性模型~([3]),将二态反应性的适用范围从生物酶催化和生物无机化学中的高价铁体系拓展到了金属有机催化化学中的低价铁催化C-H键活化领域。
In the edge area of homogeneous catalysis involving transition metals, the inert chemical bond activations by iron catalysts have attracted immense research interests.Iron, as a base metal of first row, often has multiple spin states and complicated electronic structures, which pose serious challenge on its theoretical treatment.To understand the mechanism of the inert chemical bond(such as unreactive C-H bond) activations by iron catalysts, we recently have done systematic studies covering various oxidation states of iron from 0 to +4.We found that iron catalysts with different oxidation states choose different mechanisms in C-H bond activation: Fe(0) prefers activating the C-H bond through the oxidative addition mechanism, Fe(Ⅱ)/Fe(Ⅲ) prefer s-bond metathesis pathway, while Fe(Ⅳ) employs the hydrogen atom abstraction mode.We proposed for the first time that two-state reactivity, a useful concept in C-H activation by high-valent iron, also operates in the low-valent iron systems.
In the edge area of homogeneous catalysis involving transition metals, the inert chemical bond activations by iron catalysts have attracted immense research interests.Iron, as a base metal of first row, often has multiple spin states and complicated electronic structures, which pose serious challenge on its theoretical treatment.To understand the mechanism of the inert chemical bond(such as unreactive C-H bond) activations by iron catalysts, we recently have done systematic studies covering various oxidation states of iron from 0 to +4.We found that iron catalysts with different oxidation states choose different mechanisms in C-H bond activation: Fe(0) prefers activating the C-H bond through the oxidative addition mechanism, Fe(Ⅱ)/Fe(Ⅲ) prefer s-bond metathesis pathway, while Fe(Ⅳ) employs the hydrogen atom abstraction mode.We proposed for the first time that two-state reactivity, a useful concept in C-H activation by high-valent iron, also operates in the low-valent iron systems.
引文
[1](a)Bolm,C.;Legros,J.;Le Paih,J.;Zani,L.Chem.Rev.2004,104:6217.(b)Sun,C.-L;Li,B.-J.;Shi,Z.-J.Chem.Rev.2011,111:1293.(c)Bauer,I.;Kn?lker,H.-J.;Chem.Rev.2015,115:3170.
[2]Wang,L.;Hu,L.;Zhang,H.;Chen,H.;Deng,L.J.Am.Chem.Soc.2015,137:14196.
[3]Sun,Y.;Tang,H.;Chen,K.;Hu,L.;Yao,J.;Shaik,S.;Chen,H.J.Am.Chem.Soc.2016,138:3715.
[4]Jia,T.;Zhao,C.;He,R.;Chen,H.;Wang,C.Angew.Chem.Int.Ed.2016,doi:10.1002/anie.201600365.
[2]Wang,L.;Hu,L.;Zhang,H.;Chen,H.;Deng,L.J.Am.Chem.Soc.2015,137:14196.
[3]Sun,Y.;Tang,H.;Chen,K.;Hu,L.;Yao,J.;Shaik,S.;Chen,H.J.Am.Chem.Soc.2016,138:3715.
[4]Jia,T.;Zhao,C.;He,R.;Chen,H.;Wang,C.Angew.Chem.Int.Ed.2016,doi:10.1002/anie.201600365.