Isolable Arylphosphinidene Chalcogenides and their Radical Anions
We report the synthesis, characterization, and reactivity of isolable arylphosphinidene chalcogenides (Ar─P═E; 2 (E = S), 3 (E = Se), 4 (E = Te)), prepared via chalcogen atom transfer from tris(dimethylamino)phosphine chalcogenides (Me<sub>2</sub>N)<sub>3</sub>P═E (E = S, Se, Te) to a phosphanorcaradiene. The compounds crystallize at ambient temperature and feature P═E double bonds, as confirmed by structural and computational studies. Compounds 2-4 undergo [4+2] cycloaddition with 2,3-dimethyl-1,3-butadiene to furnish six-membered heterocyclic products, demonstrating their π-bond reactivity. Compound 3 reacts with mesityl azide to afford a P(V) compound. Additionally, 2 and 3 are capable of oxidative cleavage of O─H and N─H bonds in H<sub>2</sub>O and NH<sub>3</sub>, respectively. Furthermore, 2-4 can be one-electron reduced to their corresponding radical anion salts, which are unprecedented radical anions of pnictinidene chalcogenides isolable in the condensed phase.
Authors
- Gengwen Tan (ORCID: https://orcid.org/0000-0002-6972-2197)
- Lei Xu (ORCID: https://orcid.org/0000-0002-9538-235X)
- Xinyi Li (ORCID: https://orcid.org/0000-0001-9178-5971)
- Yizhen Chen (ORCID: https://orcid.org/0009-0008-3629-0798)
- Yushuang Zhang (ORCID: https://orcid.org/0009-0001-1089-1818)
Institutions
- Sun Yat-sen University (CN)
- Jiaying University (CN)
- Nanjing University of Information Science and Technology (CN)
- Zero to Three (US)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-08-27
- DOI
- https://doi.org/10.1002/anie.202514521
- Citations
- 5
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 2.69
Funders
- National Natural Science Foundation of China
- Basic and Applied Basic Research Foundation of Guangdong Province