Phosphirene Explained

Phosphirene is the hypothetical organophosphorus compound with the formula C₂H₂PH. As the simplest cyclic, unsaturated organophosphorus compound, phosphirene is the prototype of a family of related compounds that have attracted attention from researchers.^[1]

Phosphirenes, that is substituted phosphirene compounds where one or more of the H's are replaced by organic substituents, are far more commonly discussed than the parent phosphirene. The first example of a phosphirene, 1,2,3-triphenylphosphirene was prepared via trapping of the phosphinidine complex Mo(CO)₅PPh with diphenylacetylene.^[2]

Placement of the double bond between the carbon atoms provides a 1Hphosphirene in which the phosphorus center is bonded to two carbon atoms and a hydrogen atom. Alternatively, placement of the double bond between the phosphorus center and a carbon atom generates a 2H-phosphirene. The first 2H-phosphirene was synthesized as early as 1987 by Regitz group. However, the chemistry of 2H-phosphirenes was relatively dormant until a series of reports by Stephan group.^{[3] [4]}

References

• Book: A Guide to Organophosphorus Chemistry . Quin, L. D. . Wiley-Interscience . 2000 . 0-471-31824-8 .

Notes and References

1. Encyclopedia: Comprehensive Heterocyclic Chemistry II. 1996. 277–304. 1A. Phosphiranes, Phosphirenes, and Heavier Analogues. François Mathey . Manfred Regitz . 10.1016/B978-008096518-5.00008-3. 978-0-08-096518-5.
2. Encyclopedia: J. Am. Chem. Soc.. 1982. 4484–5. 104. Generation and Trapping of Terminal Phosphinidene Complexes. Synthesis and X-ray Crystal Structure of Stable Phosphirene Complexes. Angela Marinetti . Francois Mathey . Jean Fischer . Andre Mitschler . 16. 10.1021/ja00380a029.
3. Liu. Liu Leo. Zhou. Jiliang. Cao. Levy L.. Stephan. Douglas W.. 2018-11-15. Facile Cleavage of the P=P Double Bond in Vinyl-Substituted Diphosphenes. Angewandte Chemie International Edition. en. 58. 1. 273–277. 10.1002/anie.201812592. 30444313. 53564701 . 1521-3757.
4. Liu. Liu Leo. Zhou. Jiliang. Cao. Levy L.. Andrews. Ryan. Falconer. Rosalyn L.. Russell. Christopher A.. Stephan. Douglas W.. 2017-12-22. A Transient Vinylphosphinidene via a Phosphirene–Phosphinidene Rearrangement. Journal of the American Chemical Society. en. 140. 1. 147–150. 10.1021/jacs.7b11791. 29272583. 1983/bc270929-86d1-4526-bc0b-803a533312a3 . 207187997 .