Step-growth titanium-catalysed dehydropolymerisation of amine-boranes

Precatalysts active for the dehydropolymerisation of primary amine-boranes are generally based on mid or late transition metal. We have found that the activity of the precatalyst system formed from Cp^R₂TiCl₂ and 2nBuLi towards the dehydrogenation of the secondary amine-borane Me₂NH·BH₃, to yield the cyclic diborazane [Me₂N-BH₂]₂, increases dramatically with increasing electron-donating character of the cyclopentadienyl rings (Cp^R). Application of the most active precatalyst system (Cp^R = η-C₅Me₅) to the primary amine-borane MeNH₂·BH₃ enabled the first synthesis of high molar mass poly(N-methylaminoborane), [MeNH-BH₂] , the BN analogue of polypropylene, by an early transition metal such as catalyst. Significantly, unlike other dehydropolymerization precatalysts for MeNH₂·BH₃ such as [Ir(POCOP)H₂], skeletal nickel, and [Rh(COD)Cl]₂, the Ti precatalyst system was also active towards a range of substrates including BzNH₂·BH₃ (Bz = benzyl) yielding high molar mass polymer. Moreover, in contrast to the late transition metal catalysed dehydropolymerisation of MeNH₂·BH₃ and also the Ziegler-Natta polymerisation of olefins, studies indicate that the Ti-catalyzed dehydropolymerization reactions proceed by a step-growth rather than a chain-growth mechanism.