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

The reaction of PF₅ with [(Cy₃P)₂Pt] gave the PF₃ complex trans-[(Cy₃P)₂PtF(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 [(Cy₃P)₂Pt→PF₅], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans-[(Cy₃P)₂PtF(PF₃)]⁺ was furnished by a two-step mechanism involving, successively, a second and a third PF₅ molecule.