| Abstract: | 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 S8, 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. |
