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Publication - Professor Duncan Wass

    Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs


    Metters, OJ, Forrest, SJK, Sparkes, HA, Manners, I & Wass, DF, 2016, ‘Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs’. Journal of the American Chemical Society, vol 138., pp. 1994-2003


    We report intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene aryloxide and phosphine moieties that exhibit a broad range of small molecule activation chemistry that has previously been the preserve of only intramolecular pairs. Reactions with D2, CO2, THF, and PhCCH are reported. By contrast with previous intramolecular examples, these systems allow facile access to a variety of steric and electronic characteristics at the Lewis acidic and Lewis basic components, with the three-step syntheses of 10 new intermolecular transition metal FLPs being reported. Systematic variation to the phosphine Lewis base is used to unravel steric considerations, with the surprising conclusion that phosphines with relatively small Tolman steric parameters not only give highly reactive FLPs but are often seen to have the highest selectivity for the desired product. DOSY NMR spectroscopic studies on these systems reveal for the first time the nature of the Lewis acid/Lewis base interactions in transition metal FLPs of this type.

    Full details in the University publications repository