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

^*Corresponding author for this work

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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 language	English
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	https://doi.org/10.1002/chem.201604997
Publication status	Published - 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).

Funders	Funder 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 Competitividad	CTQ2016-77558-R

Keywords

bond activation
density functional calculations
Lewis pairs
NMR spectroscopy
PF complexes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.201604997

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0 ComplexFinal published version, 1.32 MBLicence: Article 25fa Dutch Copyright Act

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

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.}",

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language = "English",

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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.

N1 - Special Issue: Cooperative Effects in Chemistry

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 - bond activation

KW - density functional calculations

KW - Lewis pairs

KW - NMR spectroscopy

KW - PF complexes

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DO - 10.1002/chem.201604997

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JF - Chemistry: A European Journal

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ER -

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

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

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CCDC 1438107: Experimental Crystal Structure Determination

Cite this

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

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1438107: Experimental Crystal Structure Determination

Cite this

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