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Six-coordinate NbF5 and TaF5 complexes with tertiary mono-phosphine and -arsine ligands

Six-coordinate NbF5 and TaF5 complexes with tertiary mono-phosphine and -arsine ligands
Six-coordinate NbF5 and TaF5 complexes with tertiary mono-phosphine and -arsine ligands
The syntheses of the extremely moisture sensitive, neutral [MF5(PR3)] (M = Nb or Ta, R = Me or Ph) and [MF5(AsR?3)] (R? = Me or Et), from reaction of the ligands with MF5 in anhydrous diethyl ether solution are reported. Attempts to isolate analogous complexes with SbMe3 were unsuccessful. The products are characterised by IR and mutinuclear NMR (1H, 19F{1H}, 31P{1H} and 93Nb) spectroscopic studies. These are the first examples of six-coordinate phosphine or arsine complexes of the Group 5 pentafluorides. The ionic species, trans-[MF4(PMe3)2][MF6], are obtained from diethyl ether solution of [MF5(PMe3)] containing excess PMe3 and similarly characterised. All complexes are extremely moisture and oxygen sensitive and decomposed by many common solvents. In solution in toluene the [MF5(PMe3)] (M = Nb or Ta) and [MF5(AsR?3)] are extensively dissociated at ambient temperatures. The [MF5(PPh3)] dissolve in CH2Cl2 with decomposition to form [PPh3H][MF6]. Attempts to isolate phosphine complexes of NbOF3 were unsuccessful.
0022-1139
62-67
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Reid, Gillian and Zhang, Wenjian (2015) Six-coordinate NbF5 and TaF5 complexes with tertiary mono-phosphine and -arsine ligands. Journal of Fluorine Chemistry, 172, 62-67. (doi:10.1016/j.jfluchem.2015.01.010).

Record type: Article

Abstract

The syntheses of the extremely moisture sensitive, neutral [MF5(PR3)] (M = Nb or Ta, R = Me or Ph) and [MF5(AsR?3)] (R? = Me or Et), from reaction of the ligands with MF5 in anhydrous diethyl ether solution are reported. Attempts to isolate analogous complexes with SbMe3 were unsuccessful. The products are characterised by IR and mutinuclear NMR (1H, 19F{1H}, 31P{1H} and 93Nb) spectroscopic studies. These are the first examples of six-coordinate phosphine or arsine complexes of the Group 5 pentafluorides. The ionic species, trans-[MF4(PMe3)2][MF6], are obtained from diethyl ether solution of [MF5(PMe3)] containing excess PMe3 and similarly characterised. All complexes are extremely moisture and oxygen sensitive and decomposed by many common solvents. In solution in toluene the [MF5(PMe3)] (M = Nb or Ta) and [MF5(AsR?3)] are extensively dissociated at ambient temperatures. The [MF5(PPh3)] dissolve in CH2Cl2 with decomposition to form [PPh3H][MF6]. Attempts to isolate phosphine complexes of NbOF3 were unsuccessful.

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Accepted/In Press date: 24 January 2015
e-pub ahead of print date: 8 February 2015
Published date: April 2015
Organisations: Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 403488
URI: https://eprints.soton.ac.uk/id/eprint/403488
ISSN: 0022-1139
PURE UUID: ec032ac5-f9d2-422a-ade4-14b61353b9e3
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 02 Dec 2016 10:20
Last modified: 03 Dec 2019 02:07

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