Abstract
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.
Original language | English |
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Pages (from-to) | 5948-5952 |
Number of pages | 5 |
Journal | Chemistry: A European Journal |
Volume | 23 |
Issue number | 25 |
Early online date | 4 Nov 2016 |
DOIs | |
Publication status | Published - 2 May 2017 |
Keywords
- bond activation
- density functional calculations
- Lewis pairs
- NMR spectroscopy
- PF complexes
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CCDC 1438107: Experimental Crystal Structure Determination
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
DOI: 10.5517/ccdc.csd.cc1k8gkv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1k8gkv&sid=DataCite
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