Structural and reactivity properties of perfluoroalkylphosphine complexes of platinum(0)

The synthesis and structural characterization of 2- and 3-coordinate Pt(0) complexes with π-acceptor perfluoroalkylphosphine ligands (PFAP’s) is reported. (dfebp)2Pt (dfebp = (C2F5)2PtBu) was prepared in moderate yield by either thermolysis of (cod)Pt(Ph)2 in neat dfebp or, more efficiently, by the treatment of (nbe)3Pt with 2 equiv. dfebp in the presence of H2. Addition of 1 equiv. CF3CO2H to (dfebp)2Pt generates the expected Pt(II) trans-(dfebp)2Pt(O2CCF3)(H) product, while treatment with the mesitylenium acid (C6Me3H4)+B(C6F5)4− leads to phosphine loss and formation of the arene complex [(η6-C6Me3H3)Pt(dfebp)(H)]+(B(C6F5)4)−. Addition of ethylene to (dfebp)2Pt results in facile and reversible equilibria with the ethylene adducts (dfebp)2Pt(C2H4) and (dfebp)Pt(C2H4)2, which have been quantified by VT NMR spectroscopy.

The first examples of structurally-characterized 2- and 3-coordinate Pt(0) complexes with π-acceptor perfluoroalkylphosphine ligands (PFAP’s) is reported. Addition of ethylene to (dfebp)2Pt (dfebp = (C2F5)2PtBu) results in facile and reversible equilibria with the ethylene adducts (dfebp)2Pt(C2H4) and (dfebp)Pt(C2H4)2.Figure optionsDownload as PowerPoint slide