Pentamethylcyclopentadienyl rhodium(III) trifluorovinyl phosphine complexes and attempted intramolecular dehydrofluorinative coupling of pentamethylcyclopentadienyl and trifluorovinyl phosphine ligands

Nicholas A. Barnes, Alan K. Brisdon, Mark Nieuwenhuyzen, Robin G. Pritchard, Graham C. Saunders

    Research output: Contribution to journalArticlepeer-review

    Abstract

    The trifluorovinyl phosphine complexes [Cp*RhCl2{PR3-x(CF{double bond, long}CF2)x}] (1 x = 1, a R = Ph, b Pri, c Et; 2 x = 2, R = Ph) have been prepared by treatment of [Cp*RhCl(μ-Cl)]2 with the relevant phosphine. The salt [Cp*RhCl(CNBut){PPh2(CF{double bond, long}CF2)}]BF4, 3, was prepared by addition of ButNC to 1a in the presence of NaBF4. The salt [Cp*RhCl{κP,κS-(CF2{double bond, long}CF)PPh(C6H4SMe-2)}]BF4 was prepared as a mixture of cis (5a) and trans (5b) isomers by treatment of [Cp*RhCl(μ-Cl)]2 with the phosphine-thioether (CF2{double bond, long}CF)PPh(C6H4SMe-2), 4, in the presence of NaBF4. The structures of 1a-c and 5a have been determined by single-crystal X-ray diffraction. Intramolecular dehydrofluorinative carbon-carbon coupling between pentamethylcyclopentadienyl and trifluorovinylphosphine ligands of 1a, 3 and 5 has been attempted. No reaction was observed on treatment of the neutral complex [Cp*RhCl2{PPh2(CF{double bond, long}CF2)}], 1a, with proton sponge, however, 5a underwent dehydrofluorinative coupling to yield [{η5,κP,κS-(C5Me4CH2CF{double bond, long}CF)PPh(C6H4SMe-2)}RhCl]BF4, 6. Other reactions, in particular addition of HF across the vinyl bonds of 5, occurred leading to a mixture of products. The cation of 3 underwent similar reactions. © 2007 Elsevier B.V. All rights reserved.
    Original languageEnglish
    Pages (from-to)943-951
    Number of pages8
    JournalJournal of Fluorine Chemistry
    Volume128
    Issue number8
    DOIs
    Publication statusPublished - Aug 2007

    Keywords

    • C-F bond cleavage
    • Dehydrofluorinative carbon-carbon coupling
    • Pentamethylcyclopentadienyl
    • Rhodium
    • Trifluorovinylphosphines

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