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Synthesis, spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands

Synthesis, spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands
Synthesis, spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands
The reaction of o-C6H4(AsMe2)2 with VCl4 in anhydrous CCl4 produces orange eight-coordinate [VCl4{o-C6H4(AsMe2)2}2], whilst in CH2Cl2 the product is the brown, six-coordinate [VCl4{o-C6H4(AsMe2)2}]. In dilute CH2Cl2 solution slow decomposition occurs to form the VIII complex [V2Cl6{o-C6H4(AsMe2)2}2].

Six-coordination is also found in [VCl4{MeC(CH2AsMe2)3}] and [VCl4{Et3As)2]. Hydrolysis of these complexes occurs readily to form vanadyl (VO2+) species, pure samples of which are obtained by reaction of [VOCl2(thf)2(H2O)] with the arsines to form green [VOCl2{o-C6H4(AsMe2)2}], [VOCl2{MeC(CH2AsMe2)3}(H2O)] and [VOCl2(Et3As)2]. Green [VOCl2(o-C6H4(PMe2)2}] is formed from [VOCl2(thf)2(H2O)] and the ligand. The [VOCl2{o-C6H4(PMe2)2}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C6H4(P(O)Me2)2}2(H2O)]Cl2, but in contrast, the products formed from similar treatment of [VCl4{o-C6H4(AsMe2)2}x] or [VOCl2{o-C6H4(AsMe2)2}] contain the novel arsenic(V) cation [o-C6H4(AsMe2Cl)(µ-O)(AsMe2)]+.

X-ray crystal structures are reported for [V2Cl6{o-C6H4(AsMe2)2}2], [VO(H2O){o-C6H4(P(O)Me2)2}2]Cl2, [o-C6H4(AsMe2Cl)(µ-O)(AsMe2)]Cl·[VO(H2O)3Cl2] and powder neutron diffraction data for [VCl4{o-C6H4(AsMe2)2}2].

Graphical abstract

Complexes of vanadium tetrachloride and vanadium oxide dichloride with a range of arsenic donors are reported, and their spectroscopic and structural characterisation described.
vanadium tetrachloride, vanadium oxide dichloride, arsine, phosphine
0277-5387
1630-1638
Gray, Benjamin M.
768c4268-32e4-436f-83d9-630f53cc464e
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Gray, Benjamin M.
768c4268-32e4-436f-83d9-630f53cc464e
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9

Gray, Benjamin M., Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael, Zhang, Wenjian and Jura, Marek (2010) Synthesis, spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands. Polyhedron, 29 (6), 1630-1638. (doi:10.1016/j.poly.2010.02.003).

Record type: Article

Abstract

The reaction of o-C6H4(AsMe2)2 with VCl4 in anhydrous CCl4 produces orange eight-coordinate [VCl4{o-C6H4(AsMe2)2}2], whilst in CH2Cl2 the product is the brown, six-coordinate [VCl4{o-C6H4(AsMe2)2}]. In dilute CH2Cl2 solution slow decomposition occurs to form the VIII complex [V2Cl6{o-C6H4(AsMe2)2}2].

Six-coordination is also found in [VCl4{MeC(CH2AsMe2)3}] and [VCl4{Et3As)2]. Hydrolysis of these complexes occurs readily to form vanadyl (VO2+) species, pure samples of which are obtained by reaction of [VOCl2(thf)2(H2O)] with the arsines to form green [VOCl2{o-C6H4(AsMe2)2}], [VOCl2{MeC(CH2AsMe2)3}(H2O)] and [VOCl2(Et3As)2]. Green [VOCl2(o-C6H4(PMe2)2}] is formed from [VOCl2(thf)2(H2O)] and the ligand. The [VOCl2{o-C6H4(PMe2)2}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C6H4(P(O)Me2)2}2(H2O)]Cl2, but in contrast, the products formed from similar treatment of [VCl4{o-C6H4(AsMe2)2}x] or [VOCl2{o-C6H4(AsMe2)2}] contain the novel arsenic(V) cation [o-C6H4(AsMe2Cl)(µ-O)(AsMe2)]+.

X-ray crystal structures are reported for [V2Cl6{o-C6H4(AsMe2)2}2], [VO(H2O){o-C6H4(P(O)Me2)2}2]Cl2, [o-C6H4(AsMe2Cl)(µ-O)(AsMe2)]Cl·[VO(H2O)3Cl2] and powder neutron diffraction data for [VCl4{o-C6H4(AsMe2)2}2].

Graphical abstract

Complexes of vanadium tetrachloride and vanadium oxide dichloride with a range of arsenic donors are reported, and their spectroscopic and structural characterisation described.

Full text not available from this repository.

More information

Published date: 19 April 2010
Keywords: vanadium tetrachloride, vanadium oxide dichloride, arsine, phosphine

Identifiers

Local EPrints ID: 148211
URI: http://eprints.soton.ac.uk/id/eprint/148211
ISSN: 0277-5387
PURE UUID: 271828ec-5c07-4f64-9a00-6e95fbb06b35
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
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: 27 Apr 2010 13:18
Last modified: 20 Jul 2019 01:28

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Contributors

Author: Benjamin M. Gray
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Michael Webster
Author: Wenjian Zhang
Author: Marek Jura

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