<i>C</i> <sub>2</sub> -Symmetric Rhenacyclobutadienes: Key Intermediates in Re(V) Alkylidyne-Catalyzed Alkyne Metathesis Reactions
Key rhenacyclobutadiene intermediates were isolated from the reactions of alkynes with a d<sup>2</sup> Re(V) alkylidyne complex (<b>5a</b>) bearing bidentate phosphinoanilide ligands. Single crystal X-ray diffraction analysis revealed a <i>pseudo</i>-<i>C</i><sub>2</sub>-symmetric structure wherein two phosphines are <i>trans</i>-oriented. These rhenacyclobutadienes can undergo [2 + 2] cycloreversion when treated with PMePh<sub>2</sub> 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<sup>0</sup> 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<sup>0</sup> alkylidynes.
Authors
- Guochen Jia (ORCID: https://orcid.org/0000-0002-4285-8756)
- Mingxu Cui (ORCID: https://orcid.org/0000-0002-3701-7696)
- Long Yiu Tsang
- Lam Cheung Kong
- Ian D. Williams
- Zhenyang Lin
- Wan Chak Lee
- Jie Huang
- Herman H. Y. Sung
Institutions
- Hong Kong University of Science and Technology (HK)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2026-02-23
- DOI
- https://doi.org/10.1021/jacs.5c20312
- Primary Topic
- Synthetic Organic Chemistry Methods
- Type
- article
- Field-Weighted Citation Impact
- 0.00