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.
- bond activation
- density functional calculations
- Lewis pairs
- NMR spectroscopy
- PF complexes
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Arnold, N. (Contributor), Bertermann, R. (Contributor), Bickelhaupt, F. (Contributor), Braunschweig, H. (Contributor), Drisch, M. (Contributor), Finze, M. (Contributor), Hupp, F. (Contributor), Poater, J. (Contributor) & Sprenger, J. A. P. (Contributor), Unknown Publisher, 1 Jan 2017