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Tertiary phosphine and arsine complexes of phosphorus pentafluoride, synthesis, properties and electronic structures

Tertiary phosphine and arsine complexes of phosphorus pentafluoride, synthesis, properties and electronic structures
Tertiary phosphine and arsine complexes of phosphorus pentafluoride, synthesis, properties and electronic structures
The reaction of PMe3 or PPh3 with PF5 in anhydrous CH2Cl2 or hexane forms the white, moisture sensitive complexes, [PF5(PR3)] (R = Me or Ph). Similar reactions involving the diphosphines, o-C6H4(PR2)2, affords the complexes [PF4{o-C6H4(PR2)2}][PF6]. The X-ray structures of [PF5(PR3)] and [PF4{o-C6H4(PMe2)2}][PF6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (1H, 19F{1H}, 31P{1H}) show that in solution in CH2Cl2/CD2Cl2 the structures determined crystallographically are the only species present for [PF5(PMe3)] and [PF4{o-C6H4(PMe2)2}][PF6], but that [PF5(PPh3)] and [PF4{o-C6H4(PPh2)2}][PF6] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex 19F{1H} and 31P{1H} NMR spectra have been analysed, including those of the cation [PF4{o-C6H4(PMe2)2}]+, which is a second order AA'XX'B2M spin system. The unstable [PF5(AsMe3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh3 nor SbEt3 form similar complexes. The electronic structures of the PF5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF5(PMe3)], [PF5(PPh3)], and [PF4{o-C6H4(PMe2)2}]+ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF5-L complexes reveal the P-L bond strength falls with L: PMe3 > PPh3 > AsMe3 consistent with the experimentally observed stabilities and in the PF5-L complexes, electron transfer from L to PF5 on forming these complexes also follows the order PMe3 > PPh3 ≈ AsMe3.
0020-1669
Dyke, John
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Emsley, James W.
f4a7252c-1410-409a-8852-5a5e03bf35e7
Greenacre, Victoria
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Levason, William
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Monzittu, Francesco
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Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
De Luca, Giuseppina
8152f554-4aa6-42bf-af23-c0d74db9f69e
Dyke, John
46393b45-6694-46f3-af20-d7369d26199f
Emsley, James W.
f4a7252c-1410-409a-8852-5a5e03bf35e7
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Monzittu, Francesco
7c94332d-ed34-4ee6-b8b3-c17c14b11849
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
De Luca, Giuseppina
8152f554-4aa6-42bf-af23-c0d74db9f69e

Dyke, John, Emsley, James W., Greenacre, Victoria, Levason, William, Monzittu, Francesco, Reid, Gillian and De Luca, Giuseppina (2020) Tertiary phosphine and arsine complexes of phosphorus pentafluoride, synthesis, properties and electronic structures. Inorganic Chemistry. (doi:10.1021/acs.inorgchem.9b03630).

Record type: Article

Abstract

The reaction of PMe3 or PPh3 with PF5 in anhydrous CH2Cl2 or hexane forms the white, moisture sensitive complexes, [PF5(PR3)] (R = Me or Ph). Similar reactions involving the diphosphines, o-C6H4(PR2)2, affords the complexes [PF4{o-C6H4(PR2)2}][PF6]. The X-ray structures of [PF5(PR3)] and [PF4{o-C6H4(PMe2)2}][PF6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (1H, 19F{1H}, 31P{1H}) show that in solution in CH2Cl2/CD2Cl2 the structures determined crystallographically are the only species present for [PF5(PMe3)] and [PF4{o-C6H4(PMe2)2}][PF6], but that [PF5(PPh3)] and [PF4{o-C6H4(PPh2)2}][PF6] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex 19F{1H} and 31P{1H} NMR spectra have been analysed, including those of the cation [PF4{o-C6H4(PMe2)2}]+, which is a second order AA'XX'B2M spin system. The unstable [PF5(AsMe3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh3 nor SbEt3 form similar complexes. The electronic structures of the PF5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF5(PMe3)], [PF5(PPh3)], and [PF4{o-C6H4(PMe2)2}]+ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF5-L complexes reveal the P-L bond strength falls with L: PMe3 > PPh3 > AsMe3 consistent with the experimentally observed stabilities and in the PF5-L complexes, electron transfer from L to PF5 on forming these complexes also follows the order PMe3 > PPh3 ≈ AsMe3.

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Accepted/In Press date: 9 March 2020
e-pub ahead of print date: 18 March 2020

Identifiers

Local EPrints ID: 438513
URI: http://eprints.soton.ac.uk/id/eprint/438513
ISSN: 0020-1669
PURE UUID: f7928ee2-6f7d-42b9-a861-f75bd09f0185
ORCID for John Dyke: ORCID iD orcid.org/0000-0002-9808-303X
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 12 Mar 2020 17:30
Last modified: 09 Mar 2021 05:01

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Contributors

Author: John Dyke ORCID iD
Author: James W. Emsley
Author: Victoria Greenacre
Author: William Levason ORCID iD
Author: Francesco Monzittu
Author: Gillian Reid ORCID iD
Author: Giuseppina De Luca

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