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Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt 0 Complex
Author(s) -
Arnold Nicole,
Bertermann Rüdiger,
Bickelhaupt F. Matthias,
Braunschweig Holger,
Drisch Michael,
Finze Maik,
Hupp Florian,
Poater Jordi,
Sprenger Jan A. P.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604997
Subject(s) - platinum , phosphorus , chemistry , radiochemistry , catalysis , organic chemistry
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.