C 2 -Symmetric Rhenacyclobutadienes: Key Intermediates in Re(V) Alkylidyne-Catalyzed Alkyne Metathesis Reactions

Journal of the American Chemical Society 2026

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Authors: Long Yiu Tsang, Mingxu Cui, Lam Cheung Kong, Jie Huang, Wan Chak Lee, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin, Guochen Jia
DOI: 10.1021/jacs.5c20312
Cited by: 2
References: 55

Abstract

Key rhenacyclobutadiene intermediates were isolated from the reactions of alkynes with a d 2 Re(V) alkylidyne complex ( 5a ) bearing bidentate phosphinoanilide ligands. Single crystal X-ray diffraction analysis revealed a pseudo - C 2 -symmetric structure wherein two phosphines are trans -oriented. These rhenacyclobutadienes can undergo [2 + 2] cycloreversion when treated with PMePh 2 or another alkyne and are able to effect internal alkyne metathesis. This work represents the first observation of reversible [2 + 2] cycloaddition reactions of alkynes with a non-d 0 alkylidyne complex, elucidates the mechanism of Re(V)-alkylidyne-catalyzed alkyne metathesis, and provides valuable insight for the rational design of new alkyne metathesis catalysts with improved activity based on non-d 0 alkylidynes.

Fields of Study & Subjects

Synthetic Organic Chemistry Methods Catalytic Alkyne Reactions Organometallic Complex Synthesis and Catalysis

Publication details

Journal / source
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Volume
148
Issue
9
Pages
9192–9198
Publication date
23 February 2026
Language
EN