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Hexahalometallate salts of trivalent scandium, yttrium and lanthanum: cation–anion association in the solid state and in solution

Hexahalometallate salts of trivalent scandium, yttrium and lanthanum: cation–anion association in the solid state and in solution
Hexahalometallate salts of trivalent scandium, yttrium and lanthanum: cation–anion association in the solid state and in solution
The hexahalide salts, [NnBu4]3[LaCl6], [BMPYRR]3[LaCl6] (BMPYRR = 1-butyl-1-methylpyrrolidinium), [EMIM]3[MX6] (EMIM = 1-ethyl-3-methylimidazolium; M = La, X = Cl, Br, I; M = Sc, Y, Ce, X = Cl) and [EDMIM]3[MX6] (EDMIM = 1-ethyl-2,3-dimethylimidazolium; M = Y, X = Cl; M = La, X = Cl, I) have been prepared and X-ray crystal structures determined for several of them, with a view to probing the effect of varying the trivalent metal ion, the halide and the counter-cation on the structures adopted in the solid state. The crystal structures of the EMIM and EDMIM salts show extensive H-bonding between the halide ligands and organic cations; based upon the H-bonding distances, this appears to be strongest for the [EMIM]3[MCl6] salts, becoming progressively weaker for heavier metal ion or halide. In terms of the cations, changing from EMIM to EDMIM also reduces the strength of the H-bonding. The strength of the cation–anion pairing in solution has also been probed in solution via NMR spectroscopy where possible (45Sc, 89Y and 189La) and, for the EMIM salts, via the shift of ?(H2) relative to [EMIM]Cl at a standard concentration. The trends observed in solution mirror those determined in the solid state.
1144-0546
7181-7189
Champion, Martin
4fecac1b-031e-45ea-ad7e-334d4da16f47
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gill
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Champion, Martin
4fecac1b-031e-45ea-ad7e-334d4da16f47
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gill
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Champion, Martin, Levason, William, Pugh, David and Reid, Gill (2016) Hexahalometallate salts of trivalent scandium, yttrium and lanthanum: cation–anion association in the solid state and in solution. New Journal of Chemistry, 40 (8), 7181-7189. (doi:10.1039/C6NJ01068G).

Record type: Article

Abstract

The hexahalide salts, [NnBu4]3[LaCl6], [BMPYRR]3[LaCl6] (BMPYRR = 1-butyl-1-methylpyrrolidinium), [EMIM]3[MX6] (EMIM = 1-ethyl-3-methylimidazolium; M = La, X = Cl, Br, I; M = Sc, Y, Ce, X = Cl) and [EDMIM]3[MX6] (EDMIM = 1-ethyl-2,3-dimethylimidazolium; M = Y, X = Cl; M = La, X = Cl, I) have been prepared and X-ray crystal structures determined for several of them, with a view to probing the effect of varying the trivalent metal ion, the halide and the counter-cation on the structures adopted in the solid state. The crystal structures of the EMIM and EDMIM salts show extensive H-bonding between the halide ligands and organic cations; based upon the H-bonding distances, this appears to be strongest for the [EMIM]3[MCl6] salts, becoming progressively weaker for heavier metal ion or halide. In terms of the cations, changing from EMIM to EDMIM also reduces the strength of the H-bonding. The strength of the cation–anion pairing in solution has also been probed in solution via NMR spectroscopy where possible (45Sc, 89Y and 189La) and, for the EMIM salts, via the shift of ?(H2) relative to [EMIM]Cl at a standard concentration. The trends observed in solution mirror those determined in the solid state.

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[LnX6]3-_salts_16_06_2016_-_final_version revised.pdf - Accepted Manuscript
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More information

Accepted/In Press date: 20 June 2016
e-pub ahead of print date: 20 June 2016
Published date: 1 August 2016
Organisations: Organic Chemistry: SCF

Identifiers

Local EPrints ID: 401725
URI: http://eprints.soton.ac.uk/id/eprint/401725
ISSN: 1144-0546
PURE UUID: 9dd0a379-ac1f-411e-a7ad-83abbed774c4
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gill Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 20 Oct 2016 13:07
Last modified: 29 Oct 2019 06:28

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