The reactivity of carbenesl and silylenes2 has occupied a prominent position in chemical research for a considerable time, and it is likely that it will continue to do so. Phosphenium ions3 (R,P+) constitute a class of molecules that may be considered as isoelectronic to carbenes and ~ilylenes.~ Although the synthesis3 and e l e c t r~n i c~~,~ and molecular5 structures of phosphenium ions have been the subject of intense investigations, their reactivity remains largely unexplored. As shown by Parry and co-workers, phosphenium ions may behave as Lewis acids or bases, as in their reactivity toward phosphines6 and metal carbonyls,' respectively. Perhaps more interestingly, Cowley and co-workers have observed the net insertion of R2P+ into a C-H bond in the reaction of [(i-Pr,N),P]+ with stannocene and plumbocene8 and the intramolecular rearrangement of [(Me5C5)(t-Bu)P]+,9 reactions that reflect the carbene character of R2P+, A well-known reaction of carbenes and silylenes is the oxidative addition of unsaturated organic compounds, but this type of reactivity is as yet unreported for R2P+. We have begun to examine this class of reactions and now report the 1,4-addition of bis(dimethy1amino)-and bis(di-ethy1amino)phosphenium tetrachloroaluminate ( l a and lb, respectively) to 1,3-butadienes (2) to form the corresponding 3phospholenium tetrachloroaluminates (3a-c).
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