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 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 “vinylide...

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Published in:Organometallics 2015-05, Vol.34 (10), p.1963-1968
Main Authors: Yeung, Chi-Fung, Chung, Lai-Hon, Lo, Hoi-Shing, Chiu, Chun-Hong, Cai, Jialin, Wong, Chun-Yuen
Format: Article
Language:English
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Summary: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.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.5b00211