Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex

Nicole Arnold, Rüdiger Bertermann, F. Matthias Bickelhaupt*, Holger Braunschweig, Michael Drisch, Maik Finze, Florian Hupp, Jordi Poater, Jan A.P. Sprenger

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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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 languageEnglish
Pages (from-to)5948-5952
Number of pages5
JournalChemistry: A European Journal
Volume23
Issue number25
Early online date4 Nov 2016
DOIs
Publication statusPublished - 2 May 2017

Bibliographical note

Special Issue: Cooperative Effects in Chemistry

Funding

This work was supported by the Deutsche Forschungsgemeinschaft, Merck KGaA, MINECO (CTQ2016-77558-R), and the Netherlands Organization for Scientific Research (NWO-CW, NWO-ALW, NWO-EW).

FundersFunder number
NWO-ALW
NWO-CW
NWO-EW
Netherlands Organization for Scientific Research
Merck KGaA
Deutsche Forschungsgemeinschaft
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y CompetitividadCTQ2016-77558-R

    Keywords

    • bond activation
    • density functional calculations
    • Lewis pairs
    • NMR spectroscopy
    • PF complexes

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