Isolation of Ruthenium–Indoline and −Indole Zwitterion Complexes: Insight into the Metal-Induced Cyclization of Aniline-Tethered Alkynes and Strategy to Lower the Activation Barrier of Metal−Vinylidene Formation
Isolation of Ruthenium–Indoline and −Indole Zwitterion Complexes: Insight into the Metal-Induced Cyclization of Aniline-Tethered Alkynes and Strategy to Lower the Activation Barrier of Metal−Vinylidene Formation
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钌-吲哚啉和-吲哚两性离子络合物的分离：深入了解金属诱导的苯胺系链炔烃的环化以及降低金属-亚乙烯基形成的活化势垒的策略
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
Chun‐Yuen Wong
中科院分区：
文献类型：
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作者：
Chi‐Fung Yeung;Lai‐Hon Chung;H. Lo;Chun;Jiali Cai;Chun‐Yuen Wong
从[Ru（[14] aneS 4）Cl 2]（[14] aneS 4 = 1，4，8，11-tetrathiacyclotetradecane）和苯胺连接的炔之间的反应中得到的Ru（II）-吲哚啉和−吲哚两性配合物的第一个例子已经分离出来。关于这些反应的“亚乙烯基参与途径”和“直接亲核闭环机制”之间的选择性的机理研究已经在实验和理论上进行。采用1，2-甲硅烷基移位作为降低形成Ru-亚乙烯基物质的活化势垒的策略也已被证明是成功的。
Isolation of the first examples of Ru(II)–indoline and −indole zwitterion complexes derived from reactions between [Ru([14]aneS4)Cl2] ([14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane) and aniline-tethered alkynes has been achieved. Mechanistic studies regarding the selectivity between a “vinylidene-involving pathway” and a “direct nucleophilic ring closure mechanism” for these reactions have been conducted experimentally and theoretically. Employment of 1,2-silyl shift as a strategy to lower the activation barrier for the formation of Ru–vinylidene species has also been proved to be successful.