Synthesis and properties of [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu) and the crystal structures of [N(n-Bu)4]3[SbS4]⋅6H2O and [N(n-Bu)4]3[Sb(S2O3)3]·2THF
Synthesis and properties of [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu) and the crystal structures of [N(n-Bu)4]3[SbS4]⋅6H2O and [N(n-Bu)4]3[Sb(S2O3)3]·2THF
The tetra-alkylammonium tetrathioantimonate(V) salts, [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu), have been prepared in basic solution from aqueous [NR4]OH, sulfur and Sb2S3, and characterised by microanalysis, IR, Raman, 1H and 121Sb NMR spectroscopy. The crystal structure of [N(n-Bu)4]3[SbS4]·6H2O shows the presence of the tetrahedral [SbS4]3− anion (disordered over two sites), and also connected through an H-bonding network with the lattice water molecules. The alkylammonium salts are soluble in water and, with the exception of [NMe4]3[SbS4], are also soluble in weakly polar organic solvents, including halocarbons and MeCN. Solubility increases with the R group Me < Et < n-Pr < n-Bu, making the [N(n-Bu)4)3[SbS4] a convenient reagent to explore coordination chemistry or materials applications for which water as the solvent is not suitable. [N(n-Bu)4]3[Sb(S2O3)3]·2THF, the first thiosulfate complex of a p-block element, was produced by slow decomposition of [N(n-Bu)4]3[SbS4] in THF solution in the presence of the [NH(n-Bu)3]Cl (as a source of H+), confirming the instability of the [SbS4]3− anion in acidic media, and the crystal structure of [N(n-Bu)4]3[Sb(S2O3)3]·2THF shows a trigonal antiprismatic coordination geometry with a S3O3 donor set at the antimony(III) centre in the anion.
King, Rhys P.
2f9548b8-fc3b-447c-a5df-de5a3e513a39
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
18 January 2023
King, Rhys P.
2f9548b8-fc3b-447c-a5df-de5a3e513a39
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
King, Rhys P., Levason, William and Reid, Gillian
(2023)
Synthesis and properties of [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu) and the crystal structures of [N(n-Bu)4]3[SbS4]⋅6H2O and [N(n-Bu)4]3[Sb(S2O3)3]·2THF.
Journal of Molecular Structure, 1278, [134925].
(doi:10.1016/j.molstruc.2023.134925).
Abstract
The tetra-alkylammonium tetrathioantimonate(V) salts, [NR4]3[SbS4] (R = Me, Et, n-Pr, n-Bu), have been prepared in basic solution from aqueous [NR4]OH, sulfur and Sb2S3, and characterised by microanalysis, IR, Raman, 1H and 121Sb NMR spectroscopy. The crystal structure of [N(n-Bu)4]3[SbS4]·6H2O shows the presence of the tetrahedral [SbS4]3− anion (disordered over two sites), and also connected through an H-bonding network with the lattice water molecules. The alkylammonium salts are soluble in water and, with the exception of [NMe4]3[SbS4], are also soluble in weakly polar organic solvents, including halocarbons and MeCN. Solubility increases with the R group Me < Et < n-Pr < n-Bu, making the [N(n-Bu)4)3[SbS4] a convenient reagent to explore coordination chemistry or materials applications for which water as the solvent is not suitable. [N(n-Bu)4]3[Sb(S2O3)3]·2THF, the first thiosulfate complex of a p-block element, was produced by slow decomposition of [N(n-Bu)4]3[SbS4] in THF solution in the presence of the [NH(n-Bu)3]Cl (as a source of H+), confirming the instability of the [SbS4]3− anion in acidic media, and the crystal structure of [N(n-Bu)4]3[Sb(S2O3)3]·2THF shows a trigonal antiprismatic coordination geometry with a S3O3 donor set at the antimony(III) centre in the anion.
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Accepted/In Press date: 4 January 2023
e-pub ahead of print date: 6 January 2023
Published date: 18 January 2023
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Funding Information:
We thank the EPSRC for funding through grants EP/P025137/1 and EP/N035437/1.
Identifiers
Local EPrints ID: 475516
URI: http://eprints.soton.ac.uk/id/eprint/475516
ISSN: 0022-2860
PURE UUID: 159dcd83-f97a-4233-a2e3-e7268871cc88
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Date deposited: 21 Mar 2023 17:33
Last modified: 28 Aug 2024 01:33
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Author:
Rhys P. King
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