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Publication - Professor Paul Pringle

    Ring size effects in cyclic fluorophosphites

    ligands that span the bonding space between phosphites and PF3

    Citation

    Miles-Hobbs, AM, Hunt, E, Pringle, PG & Sparkes, HA, 2019, ‘Ring size effects in cyclic fluorophosphites: ligands that span the bonding space between phosphites and PF3’. Dalton Transactions, vol 48., pp. 9712-9724

    Abstract

    The 5- to 8-membered cyclic fluorophosphites L5-8 have been prepared from the corresponding chlorophosphites which are derived from dihydroxyarenes or bis(trimethylsiloxy)arenes. Ligand L5 is very sensitive to hydrolysis but L6-8 are much more kinetically robust. The coordination chemistry of L5-8 has been explored with Mo(0), Pt(0) and Rh(i) and it is shown that the π-acceptor properties of L5-8 increase with decreasing ring size. The IR spectra and X-ray crystal structures of the [Mo(CO)4L2] complexes show that L5-8 lie between PF3 and P(OAr)3 in terms of their σ/π-bonding properties. The [PtL4] complexes are readily prepared from [Pt(nbe)3] and 4 equiv. of L5-8 whereas equilibrium mixtures of PtLx(nbe)y species form when 2 equiv. of L5-8 are added to [Pt(nbe)3]. The CO substitution reactions of [Rh2Cl2(CO)4] with L5-8 to give [Rh2Cl2L4] are evidence of the PF3-like ligand properties of L5-8. The trends in the properties of L5-8 are analysed in terms of their proximity to PF3 or P(OPh)3.

    Full details in the University publications repository