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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 PMe 3 or PPh 3 with PF 5 in anhydrous CH 2Cl 2 or hexane forms the white, moisture-sensitive complexes [PF 5(PR 3)] (R = Me, Ph). Similar reactions involving the diphosphines o-C 6H 4(PR 2) 2 afford the complexes [PF 4{o-C 6H 4(PR 2) 2}][PF 6]. The X-ray structures of [PF 5(PR 3)] and [PF 4{o-C 6H 4(PMe 2) 2}][PF 6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra ( 1H, 19F{ 1H}, 31P{ 1H}) show that in solution in CH 2Cl 2/CD 2Cl 2 the structures determined crystallographically are the only species present for [PF 5(PMe 3)] and [PF 4{o-C 6H 4(PMe 2) 2}][PF 6] but that [PF 5(PPh 3)] and [PF 4{o-C 6H 4(PPh 2) 2}][PF 6] 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 analyzed, including those of the cation [PF 4{o-C 6H 4(PMe 2) 2}] +, which is a second-order AA′XX′B 2M spin system. The unstable [PF 5(AsMe 3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh 3 nor SbEt 3 forms similar complexes. The electronic structures of the PF 5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF 5(PMe 3)], [PF 5(PPh 3)], and [PF 4{o-C 6H 4(PMe 2) 2}] + are in good agreement with their respective crystal structure geometries. DFT calculations on the PF 5-L complexes reveal the P-L bond strength falls with L in the order PMe 3 > PPh 3 > AsMe 3, consistent with the experimentally observed stabilities, and in the PF 5-L complexes, electron transfer from L to PF 5 on forming these complexes also follows the order PMe 3 > PPh 3 ≈ AsMe 3.

0020-1669
4517-4526
Dyke, John
46393b45-6694-46f3-af20-d7369d26199f
Emsley, James W.
f4a7252c-1410-409a-8852-5a5e03bf35e7
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Levason, William
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Monzittu, Francesco
7c94332d-ed34-4ee6-b8b3-c17c14b11849
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, 59 (7), 4517-4526. (doi:10.1021/acs.inorgchem.9b03630).

Record type: Article

Abstract

The reaction of PMe 3 or PPh 3 with PF 5 in anhydrous CH 2Cl 2 or hexane forms the white, moisture-sensitive complexes [PF 5(PR 3)] (R = Me, Ph). Similar reactions involving the diphosphines o-C 6H 4(PR 2) 2 afford the complexes [PF 4{o-C 6H 4(PR 2) 2}][PF 6]. The X-ray structures of [PF 5(PR 3)] and [PF 4{o-C 6H 4(PMe 2) 2}][PF 6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra ( 1H, 19F{ 1H}, 31P{ 1H}) show that in solution in CH 2Cl 2/CD 2Cl 2 the structures determined crystallographically are the only species present for [PF 5(PMe 3)] and [PF 4{o-C 6H 4(PMe 2) 2}][PF 6] but that [PF 5(PPh 3)] and [PF 4{o-C 6H 4(PPh 2) 2}][PF 6] 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 analyzed, including those of the cation [PF 4{o-C 6H 4(PMe 2) 2}] +, which is a second-order AA′XX′B 2M spin system. The unstable [PF 5(AsMe 3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh 3 nor SbEt 3 forms similar complexes. The electronic structures of the PF 5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF 5(PMe 3)], [PF 5(PPh 3)], and [PF 4{o-C 6H 4(PMe 2) 2}] + are in good agreement with their respective crystal structure geometries. DFT calculations on the PF 5-L complexes reveal the P-L bond strength falls with L in the order PMe 3 > PPh 3 > AsMe 3, consistent with the experimentally observed stabilities, and in the PF 5-L complexes, electron transfer from L to PF 5 on forming these complexes also follows the order PMe 3 > PPh 3 ≈ AsMe 3.

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Accepted/In Press date: 9 March 2020
e-pub ahead of print date: 18 March 2020
Published date: 6 April 2020
Additional Information: Funding Information: We thank the EPSRC for support (EP/P025137/1 and EP/R513325/1) and Dr. M. E. Light for assistance with modeling the disorder in the [PF5(PMe3)] crystal structure. Publisher Copyright: © 2020 American Chemical Society.
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Identifiers

Local EPrints ID: 438513
URI: http://eprints.soton.ac.uk/id/eprint/438513
DOI: doi:10.1021/acs.inorgchem.9b03630
ISSN: 0020-1669
PURE UUID: f7928ee2-6f7d-42b9-a861-f75bd09f0185
ORCID for John Dyke: ORCID iD orcid.org/0000-0002-9808-303X
ORCID for Victoria Greenacre: ORCID iD orcid.org/0000-0002-3381-9616
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: 17 Mar 2024 05:24

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Contributors

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

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