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

Abstract

The synthesis and structural characterization of 2-and 3-coordinate Pt(0) complexes with -acceptor perfluoroalkylphosphine ligands (PFAP's) is reported. (dfebp) 2 Pt (dfebp = (C 2 F 5) 2 P t Bu) was prepared in moderate yield by either thermolysis of (cod)Pt(Ph) 2 in neat dfebp or, more efficiently, by the treatment of (nbe) 3 Pt with 2 equiv. dfebp in the presence of H 2. Addition of 1 equiv. CF 3 CO 2 H to (dfebp) 2 Pt generates the expected Pt(II) trans-(dfebp) 2 Pt(O 2 CCF 3)(H) product, while treatment with the mesitylenium acid (C 6 Me 3 H 4) + B(C 6 F 5) 4 leads to phosphine loss and formation of the arene complex [( 6-C 6 Me 3 H 3)Pt(dfmp)(CH 3)] + (B(C 6 F 5) 4)-. Addition of ethylene to (dfebp) 2 Pt results in facile and reversible equilibria with the ethylene adducts (dfebp) 2 Pt(C 2 H 4) and (dfebp)Pt(C 2 H 4) 2 , which have been quantified by VT NMR spectroscopy.