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

doi:10.1002/chem.201604997

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

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

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
Pages (from-to)	5948-5952
Number of pages	5
Journal	Chemistry - A European Journal
Volume	23
Issue number	25
DOIs	https://doi.org/10.1002/chem.201604997
Publication status	Published - 2 May 2017
Externally published	Yes

Keywords

Lewis pairs
NMR spectroscopy
PF complexes
bond activation
density functional calculations

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201604997

Cite this

@article{aedfcdf9cc11483bacf40ca4cd68881b,

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

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.",

keywords = "Lewis pairs, NMR spectroscopy, PF complexes, bond activation, density functional calculations",

author = "Nicole Arnold and R{\"u}diger Bertermann and Bickelhaupt, \{F. Matthias\} and Holger Braunschweig and Michael Drisch and Maik Finze and Florian Hupp and Jordi Poater and Sprenger, \{Jan A.P.\}",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = may,

day = "2",

doi = "10.1002/chem.201604997",

language = "English",

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T1 - Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 Complex

AU - Arnold, Nicole

AU - Bertermann, Rüdiger

AU - Bickelhaupt, F. Matthias

AU - Braunschweig, Holger

AU - Drisch, Michael

AU - Finze, Maik

AU - Hupp, Florian

AU - Poater, Jordi

AU - Sprenger, Jan A.P.

PY - 2017/5/2

Y1 - 2017/5/2

N2 - 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.

AB - 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.

KW - Lewis pairs

KW - NMR spectroscopy

KW - PF complexes

KW - bond activation

KW - density functional calculations

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DO - 10.1002/chem.201604997

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JO - Chemistry - A European Journal

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