Abstract
The phosphino‐phosphonium cations of the form [R3PPR’2]+ are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair‐type addition reactions to alkynes, affording unprecedented phosphino‐phosphination reactions and giving cations of the form [cis‐R3PCHC(R”)PR’2]+. This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis‐olefin‐linked bidentate phosphines.
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