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Updated: Jun 24, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Isomerization reactions of metal vinylidene units
Xuejuan Zheng1, Fanping Huang1, Xinyuan Li1
1Shenzhen Grubbs Institute, Department of Chemistry, Guangming Advanced Research Institute, Southern University of Science and Technology Shenzhen 518055 China luom3@sustech.edu.cn xiahp@sustech.edu.cn.
Abstract:
Isomerization reactions of unsaturated molecules offer an efficient strategy in atom-economical synthesis. Although isomerization reactions of unsaturated organic and organometallic compounds, such as alkenes, alkynes, and metal carbynes, have been achieved, those of metal vinylidene units that contain cumulated double bonds have never been reported. Herein, we inaugurally discovered isomerization reactions of metal vinylidene units via protonation and deprotonation reactions of metal carbenes. Experimental and theoretical investigations indicate that the electrical characteristics of substituents on the rings play a crucial role in controlling the formation of metal vinylidene units. The isomerization reactions of metal vinylidene units were driven by thermodynamic forces. Moreover, one of the angles at metal vinylidenes was found as 126.9°, representing the smallest angle in metal vinylidenes and the first cyclic 4d transition metal (Ru) vinylidene complex was successfully isolated. These investigations unveil novel structures and reactivity for metal vinylidenes, offering a fresh perspective on the isomerization reactions of unsaturated molecules containing cumulative unsaturated bonds.
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