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Facile Cleavage of the P=P Double Bond in Vinyl‐Substituted Diphosphenes
Author(s) -
Liu Liu Leo,
Cao Levy L.,
Zhou Jiliang,
Stephan Douglas W.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201812592
Subject(s) - carbene , cationic polymerization , chemistry , bond cleavage , double bond , cleavage (geology) , ion , alkyl , medicinal chemistry , polymer chemistry , stereochemistry , organic chemistry , catalysis , materials science , fracture (geology) , composite material
The reactions of the cyclic alkyl amino carbene (CAAC) 1 with phosphaalkynes generate the kinetically unstable CAAC‐derived phosphirenes 4 and 5 , which undergo rearrangement/dimerization reactions to give the vinyl‐substituted diphosphenes 2 , 3 , and 6 . The P=P double bond scission of 2 or 3 is unprecedentedly effected by S 8 , [AuCl(tht)], or MeOTf at room temperature, which affords a dithiophosphorane 7 , a phosphepine Au complex 8 , or phosphepinium cations 9 and 10 , respectively. The cationic species feature little homoaromaticity while representing the first examples of the phosphorus‐containing analogue of the tropylium ion.