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Publication - Professor Ian Manners

    Metal-free dehydropolymerisation of phosphine-boranes using cyclic (alkyl)(amino)carbenes as hydrogen acceptors


    Oldroyd, NL, Chitnis, SS, Annibale, VT, Arz, MI, Sparkes, HA & Manners, I, 2019, ‘Metal-free dehydropolymerisation of phosphine-boranes using cyclic (alkyl)(amino)carbenes as hydrogen acceptors’. Nature Communications, vol 10., pp. 1370


    The divalent carbene carbon centre in cyclic (alkyl)(amino)carbenes (CAACs) is known to exhibit transition-metal like insertion into E–H -bonds (E = H, N, Si, B, P, C, O) with formation of new, strong C–E and C–H bonds. Although subsequent transformations of the products represent an attractive strategy for metal-free synthesis, few examples have been reported. Herein we describe the dehydrogenation of phosphine-boranes, RR’PH·BH3, using a CAAC, which behaves as a stoichiometric hydrogen acceptor to release monomeric phosphinoboranes, [RR’P-BH2], under mild conditions. The latter species are transient intermediates that either polymerise to the corresponding polyphosphinoboranes, [RR’PBH2]n (R = Ph; R’ = H, Ph or Et), or are trapped in the form of CAAC-phosphinoborane adducts, CAAC·H2BPRR’ (R = R’ = tBu; R = R’ = Mes). In contrast to previously established methods such as transition metal-catalysed dehydrocoupling, which only yield P-monosubstituted polymers, [RHPBH2]n, the CAAC-mediated route also provides access to P-disubstituted polymers, [RR’PBH2]n (R= Ph; R’ = Ph or Et).

    Full details in the University publications repository