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Publication - Professor Duncan Wass

    Zirconium-Nitrogen Intramolecular Frustrated Lewis Pairs


    Hamilton, H, King, A, Sparkes, H, Pridmore, N & Wass, D, 2019, ‘Zirconium-Nitrogen Intramolecular Frustrated Lewis Pairs’. Inorganic Chemistry, vol 58., pp. 6399-6409


    A series of intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene alkoxide complexes ([Cp2Zr(OMes)]+ 1 or ([Cp*2Zr(OMes)]+ 2) with nitrogen Lewis bases (NEt3, NEtiPr2,
    pyridine, 2-methylpyridine, 2,6-lutidine) are reported. The interaction
    between Zr and N depends on the specific derivatives used, in general
    more sterically encumbered pairs leading to a more frustrated
    interaction; however, DOSY NMR spectroscopy reveals these interactions
    to be dynamic in nature. The pairs undergo typical FLP-type reactivity
    with D2, CO2, THF, and PhCCD. The catalytic dehydrocoupling of Me2NH·BH3
    is also reported. Comparisons can be made with previous work employing
    phosphines as Lewis bases suggesting that hard–hard or hard–soft
    acid–base considerations are of little importance compared to the more
    prominent roles of steric bulk and basicity.

    Full details in the University publications repository