Issue 22, 2024

Isomerization reactions of metal vinylidene units

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.

Graphical abstract: Isomerization reactions of metal vinylidene units

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Mar 2024
Accepted
29 Apr 2024
First published
03 May 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 8443-8450

Isomerization reactions of metal vinylidene units

X. Zheng, F. Huang, X. Li, K. Zhuo, D. Chen, M. Luo and H. Xia, Chem. Sci., 2024, 15, 8443 DOI: 10.1039/D4SC01993H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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