Formation of a Trifluorophosphane Platinum(II) Complex by P-F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex.

The reaction of PF5 with [(Cy3 P)2 Pt] gave the PF3 complex trans-[(Cy3 P)2 PtF(PF3 )][PF6 ], which was characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy, and elemental analysis. To the best of our knowledge, this reaction is the first example of the oxidative addition of a P-F bond to a transition metal and is a rare example of an activation of a main-group-element-fluorine bond by a metal. Relativistic DFT calculations showed that the formation of the Lewis pair [(Cy3 P)2 Pt→PF5 ], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans-[(Cy3 P)2 PtF(PF3 )]+ was furnished by a two-step mechanism involving, successively, a second and a third PF5 molecule.