Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt 0 Complex

The reaction of PF 5 with [(Cy 3 P) 2 Pt] gave the PF 3 complex trans ‐[(Cy 3 P) 2 PtF(PF 3 )][PF 6 ], 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 [(Cy 3 P) 2 Pt→PF 5 ], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans ‐[(Cy 3 P) 2 PtF(PF 3 )] + was furnished by a two‐step mechanism involving, successively, a second and a third PF 5 molecule.