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Publication - Professor Duncan Wass

    Catalytic dehydrocoupling of Amine-Boranes Using Cationic Zirconium(IV)-Phosphine Frustrated Lewis Pairs

    Citation

    Metters, OJ, Flynn, SR, Dowds, C, Sparkes, HA, Manners, I & Wass, DF, 2016, ‘Catalytic dehydrocoupling of Amine-Boranes Using Cationic Zirconium(IV)-Phosphine Frustrated Lewis Pairs’. ACS Catalysis, vol 6., pp. 6601-6611

    Abstract

    A series of novel, intramolecular Zr(IV)/P frustrated Lewis pairs (FLPs) based on cationic zirconocene fragments with a variety of ancillary cyclopentadienyl and 2-
    phosphinoaryloxide (−O(C6H4)PR2, R = tBu and 3,5-CF3- (C6H3)) ligands are reported and their activity as catalysts for the dehydrocoupling of dimethylamine−borane (Me2NH·BH3) assessed. The FLP system [(C9H7)2ZrO(C6H4)PtBu2]-[B(C6F5)4] is shown to give unprecedented turnover
    frequencies (TOF) for a catalyst based on a group 4 metal (TOF ≥ 600 h−1), while also proving to be the most efficient FLP catalyst reported to date. The mechanism of this reaction has been probed using analogous intermolecular Zr(IV)/P FLPs, permitting deconvolution of the reactions taking place at both the Lewis acidic and basic sites. Elucidation of this mechanism revealed an interesting cooperative two-cycle process where one cycle is FLP mediated and the other, a redistribution of a linear diborazane intermediate, relies solely on the presence of a Zr(IV) Lewis acid.

    Full details in the University publications repository