Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex. Issue 25 (22nd November 2016)

• Record Type: Journal Article
• Authors: Arnold, Nicole; Bertermann, Rüdiger; Bickelhaupt, F. Matthias; Braunschweig, Holger; Drisch, Michael; Finze, Maik; Hupp, Florian; Poater, Jordi; Sprenger, Jan A. P.
• Is Part Of: Chemistry. Volume 23:Issue 25(2017)
• Page Start: 5948
• Page End: 5952
• Publication Date: 2016-11-22
• Subjects: bond activation -- density functional calculations -- Lewis pairs -- NMR spectroscopy -- PF3 complexes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201604997
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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. Abstract : Activate me ! trans ‐[(Cy3 P)2 PtF(PF3 )][PF6 ] was obtained by the reaction of PF5 with [(Cy3 P)2 Pt]. Most likely, the first step of the reaction is the formation of the Lewis pair [(Cy3 P)2 Pt→PF5 ] 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).