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)2PtPF5], 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. Activate me! trans-[(Cy3P)2PtF(PF3)][PF6] was obtained by the reaction of PF5 with [(Cy3P)2Pt]. Most likely, the first step of the reaction is the formation of the Lewis pair [(Cy3P)2PtPF5] followed by an unprecedented P−F bond activation, which represents a very rare example of activation of a main-group-element–fluorine bond (see scheme).

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pf3 complex twostep mechanism maingroupelementfluorine bond lewis pair

Nicole Arnold, Rüdiger Bertermann, Florian Hupp, F. Matthias Bickelhaupt, Jan A. P. Sprenger, Holger Braunschweig, Michael Drisch, Maik Finze, Jordi Poater,.Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex. 23 (25),5952-5948.

Nicole Arnold, et al."Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex" 23

Nicole Arnold, Rüdiger Bertermann, Florian Hupp, F. Matthias Bickelhaupt, Jan A. P. Sprenger, Holger Braunschweig, Michael Drisch, Maik Finze, Jordi Poater,"Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex"