The coordination chemistry of perfluorovinyl substituted phosphine ligands, a crystallographic and spectroscopic study. Co-crystallisation of both cis- and trans-isomers of [PtCl2{PiPr2(CFCF 2)}2] within the same unit cell

Nicholas A. Barnes, Alan K. Brisdon, F. R William Brown, Wendy I. Cross, Christopher J. Herbert, Robin G. Pritchard, Ghazala Sadiq

    Research output: Contribution to journalArticlepeer-review

    Abstract

    The coordination chemistry of the perfluorovinyl phosphines PEt 2(CFCF2), PiPr2(CFCF2), PCy2(CFCF2) and PPh(CFCF2)2 to rhodium(i), palladium(ii), and platinum(ii) centres has been investigated. The electronic properties of the ligands are estimated based on ν(CO) and 1J(Rh-P) values. X-Ray diffraction data for the square-planar Pd(ii) and Pt(ii) perfluorovinyl-phosphine containing complexes allow estimates of the steric demand for the series of ligands PPh2(CFCF2), PEt2(CFCF2), PiPr2(CFCF 2), PCy2(CFCF2) and PPh(CFCF2) 2 to be determined. The (CFCF2) fragment is found to be more electron withdrawing than (C6F5) yet sterically less demanding. These ligands therefore provide a range of electron-neutral to phosphite-like electronic properties combined with a range of steric demands. This study also reveals that short intramolecular interactions from the metal centre to the β-fluorine atom cis to phosphorus of the CFCF2 groups are observed in all-trans square planar complexes of the ligands. Unusually, the complex [PtCl2{PiPr2(CFCF 2)}2] crystallises with both cis- and trans-isomers present in the unit cell. It appears that co-crystallisation of both isomers occurs in order to maximise fluorous regions in the crystal packing, and the extended structure displays short fluorine-fluorine contacts. The generation of mixed geometries seems to be a phenomenon of crystallisation, as solution phase NMR studies reveal the presence of only the trans-isomer. © The Royal Society of Chemistry.
    Original languageEnglish
    Pages (from-to)101-114
    Number of pages13
    JournalDalton Transactions
    Issue number1
    DOIs
    Publication statusPublished - 2008

    Keywords

    • Crystal structure
    • Molecular structure (of rhodium(I), palladium(II) and platinum(II) complexes with perfluorovinyl substituted phosphine ligands)
    • Transition metal complexes Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (phosphine
    • prepn. and crystal structure of rhodium(I), palladium(II) and platinum(II) complexes with perfluorovinyl substituted phosphine ligands)
    • Phosphines Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (transition metal complexes
    • rhodium palladium platinum perfluorovinyl phosphine prepn structure
    • crystal structure rhodium palladium platinum perfluorovinyl phosphine

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