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Three reactions of phosphanylphosphaalkene (1) with nucleophiles were performed to activate the diphosphorus monomer. We observed similar results in the reactions with MeLi and nBuLi, in which the P-P bond is cleavaged and triphosphorus systems [P(Me)2-CH(biph)-CH(biph)-P-(PtBu2)]- (1a'' and [P(nBu)2-CH(biph)-CH(biph)-P-(PtBu2)]- (1b'', respectively, are formed depending on the nucleophilic reagent (biph = biphenyl). In the case of tBuLi, the P-P bond remains intact; on the phosphorus atom, only one -tBu group is substituted, and as