Transition‐Metal‐Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature

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Stoichiometric reaction of phosphine–borane adducts RR'PH⋅BH3 (R=Ph, R’=H, Ph, Et, and R=R’=tBu) with the strong acid HNTf2 (Tf=SO2CF3) leads to H2 elimination and the formation of the triflimido derivatives, RR'PH⋅BH2(NTf2). Subsequent deprotonation by using bases, such as diisopropylethylamine or the carbene IPr (IPr=N,N’‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), led to the formation of P‐mono‐ or ‐disubstituted polyphosphinoboranes [RR'P‐BH2]n. Evidence for the intermediacy of transient phosphinoborane monomers, RR'PBH2, was provided by trapping reactions.