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Soft diphosphine and diarsine complexes of niobium(v) and tantalum(v) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides

Soft diphosphine and diarsine complexes of niobium(v) and tantalum(v) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides
Soft diphosphine and diarsine complexes of niobium(v) and tantalum(v) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides
The reactions of the soft diphosphines o-C6H4(PMe2)2, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2 or o-C6H4(PPh2)2 with NbF5 or TaF5 in anhydrous MeCN solution produce [MF4(diphosphine)2][MF6] (M = Nb or Ta), which have been characterised by microanalysis, IR, 1H, 19F{1H}, 31P{1H} and 93Nb NMR spectroscopy. X-ray crystal structures are reported for the isomorphous [MF4{o-C6H4(PMe2)2}2][MF6], which confirm the presence of eight-coordinate (distorted dodecahedral) cations. The corresponding reactions using o-C6H4(AsMe2)2 produced [MF4{o-C6H4(AsMe2)2}2][MF6] which were similarly characterised, including by the X-ray structure of [NbF4{o-C6H4(AsMe2)2}2][NbF6]. These are very rare examples of arsine complexes of high valent metal fluorides. The chloro complexes [NbCl4{o-C6H4(PMe2)2}2]Cl, [TaCl4{o-C6H4(PMe2)2}2][TaCl6], [NbCl4{Me2P(CH2)2PMe2}2][NbCl6] and [MCl4{o-C6H4(AsMe2)2}2][MCl6] were prepared and their structural and spectroscopic properties compared with the fluoride analogues. Attempts to prepare diphosphine complexes of NbOF3 were unsuccessful, but the NbOCl3 complexes, [{{Me2P(CH2)2PMe2}NbOCl3}2{?-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(?-O)NbCl3(CH3CN){o-C6H4(PMe2)2}] were obtained. X-Ray structures are also reported for [NbCl4{o-C6H4(PMe2)2}2]Cl, [NbCl4{o-C6H4(AsMe2)2}2][NbCl5(OEt)], [NbCl4{o-C6H4(PMe2)2}2][NbOCl4(CH3CN)], [{{Me2P(CH2)2PMe2}NbOCl3}2{?-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(?-O)NbCl3(CH3CN){o-C6H4(PMe2)2}].
0300-9246
9557-9566
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Light, Mark, Reid, Gillian and Zhang, Wenjian (2014) Soft diphosphine and diarsine complexes of niobium(v) and tantalum(v) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides. Dalton Transactions, 43 (25), 9557-9566. (doi:10.1039/c4dt01029a).

Record type: Article

Abstract

The reactions of the soft diphosphines o-C6H4(PMe2)2, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2 or o-C6H4(PPh2)2 with NbF5 or TaF5 in anhydrous MeCN solution produce [MF4(diphosphine)2][MF6] (M = Nb or Ta), which have been characterised by microanalysis, IR, 1H, 19F{1H}, 31P{1H} and 93Nb NMR spectroscopy. X-ray crystal structures are reported for the isomorphous [MF4{o-C6H4(PMe2)2}2][MF6], which confirm the presence of eight-coordinate (distorted dodecahedral) cations. The corresponding reactions using o-C6H4(AsMe2)2 produced [MF4{o-C6H4(AsMe2)2}2][MF6] which were similarly characterised, including by the X-ray structure of [NbF4{o-C6H4(AsMe2)2}2][NbF6]. These are very rare examples of arsine complexes of high valent metal fluorides. The chloro complexes [NbCl4{o-C6H4(PMe2)2}2]Cl, [TaCl4{o-C6H4(PMe2)2}2][TaCl6], [NbCl4{Me2P(CH2)2PMe2}2][NbCl6] and [MCl4{o-C6H4(AsMe2)2}2][MCl6] were prepared and their structural and spectroscopic properties compared with the fluoride analogues. Attempts to prepare diphosphine complexes of NbOF3 were unsuccessful, but the NbOCl3 complexes, [{{Me2P(CH2)2PMe2}NbOCl3}2{?-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(?-O)NbCl3(CH3CN){o-C6H4(PMe2)2}] were obtained. X-Ray structures are also reported for [NbCl4{o-C6H4(PMe2)2}2]Cl, [NbCl4{o-C6H4(AsMe2)2}2][NbCl5(OEt)], [NbCl4{o-C6H4(PMe2)2}2][NbOCl4(CH3CN)], [{{Me2P(CH2)2PMe2}NbOCl3}2{?-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(?-O)NbCl3(CH3CN){o-C6H4(PMe2)2}].

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Published date: 7 May 2014
Organisations: Chemistry

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Local EPrints ID: 368636
URI: http://eprints.soton.ac.uk/id/eprint/368636
ISSN: 0300-9246
PURE UUID: 09be765d-c931-40ed-8c9a-e84c5079bbf2
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 06 Sep 2014 12:53
Last modified: 18 Feb 2021 16:52

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Author: William Levason ORCID iD
Author: Mark Light ORCID iD
Author: Gillian Reid ORCID iD
Author: Wenjian Zhang

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