Lanthanide tri- and tetrathionates and their complexes with triphenylphosphine oxide
Lanthanide tri- and tetrathionates and their complexes with triphenylphosphine oxide
Lanthanide tri- and tetrathionate containing species have been prepared in solution by the reaction of potassium tri- and tetrathionate with lanthanide perchlorates. Unstable solid materials from these reactions have been examined by infrared spectroscopy and electrospray mass spectrometry (ESI MS). There was evidence of the formation of S3O62− and S4O62− coordination to lanthanide ions, but it was not possible to produce material suitable for single crystal X-ray studies. The reaction of ethanol solutions from Ln(ClO4)3/K2SnO6 (n = 3,4) with triphenylphosphine oxide yielded crystalline materials which have been characterised by infrared spectroscopy, electrospray mass spectrometry, elemental analysis and single crystal X-ray diffraction. The trithionate complexes [Ln(S3O6)(Ph3PO)4]ClO4·3H2O (Ln = Nd, Tb) have been isolated. The tetrathionate/Ph3PO reaction gave rise to significant disproportionation giving a small quantity of [Nd(S4O6)(Ph3PO)4(H2O)]ClO4, a different isomer of [Nd(S3O6)(Ph3PO)4H2O]ClO4, neodymium sulfate and elemental sulfur. The crystal structures of the two isomers of [Nd(S3O6)(Ph3PO)4H2O]ClO4 and that of [Nd(S4O6)(Ph3PO)4H2O]ClO4 are reported. The structure of [Er(H2O)5(Ph3PO)2].5Ph3PO.3[ClO4], formed during the attempted preparation of erbium trithionate complexes, is also described.
Lanthanide, Polythionate structures, Triphenylphosphine oxide
Coles, Simon J.
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Fieldhouse, Sarah J.
c03807d2-a231-4f5d-8ad4-157e1b1b4689
Klooster, Wim
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Lees, Anthony M.J.
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Platt, Andrew W.G.
5c37ba32-808b-4cfd-beab-f42c8c806a61
15 March 2020
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Fieldhouse, Sarah J.
c03807d2-a231-4f5d-8ad4-157e1b1b4689
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Lees, Anthony M.J.
d0525bcc-cbd9-4f7d-8a28-f4bb70f8d997
Platt, Andrew W.G.
5c37ba32-808b-4cfd-beab-f42c8c806a61
Coles, Simon J., Fieldhouse, Sarah J., Klooster, Wim, Lees, Anthony M.J. and Platt, Andrew W.G.
(2020)
Lanthanide tri- and tetrathionates and their complexes with triphenylphosphine oxide.
Polyhedron, 179, [114404].
(doi:10.1016/j.poly.2020.114404).
Abstract
Lanthanide tri- and tetrathionate containing species have been prepared in solution by the reaction of potassium tri- and tetrathionate with lanthanide perchlorates. Unstable solid materials from these reactions have been examined by infrared spectroscopy and electrospray mass spectrometry (ESI MS). There was evidence of the formation of S3O62− and S4O62− coordination to lanthanide ions, but it was not possible to produce material suitable for single crystal X-ray studies. The reaction of ethanol solutions from Ln(ClO4)3/K2SnO6 (n = 3,4) with triphenylphosphine oxide yielded crystalline materials which have been characterised by infrared spectroscopy, electrospray mass spectrometry, elemental analysis and single crystal X-ray diffraction. The trithionate complexes [Ln(S3O6)(Ph3PO)4]ClO4·3H2O (Ln = Nd, Tb) have been isolated. The tetrathionate/Ph3PO reaction gave rise to significant disproportionation giving a small quantity of [Nd(S4O6)(Ph3PO)4(H2O)]ClO4, a different isomer of [Nd(S3O6)(Ph3PO)4H2O]ClO4, neodymium sulfate and elemental sulfur. The crystal structures of the two isomers of [Nd(S3O6)(Ph3PO)4H2O]ClO4 and that of [Nd(S4O6)(Ph3PO)4H2O]ClO4 are reported. The structure of [Er(H2O)5(Ph3PO)2].5Ph3PO.3[ClO4], formed during the attempted preparation of erbium trithionate complexes, is also described.
Text
Polyhedron 2020
- Accepted Manuscript
More information
Accepted/In Press date: 24 January 2020
e-pub ahead of print date: 28 January 2020
Published date: 15 March 2020
Keywords:
Lanthanide, Polythionate structures, Triphenylphosphine oxide
Identifiers
Local EPrints ID: 438050
URI: http://eprints.soton.ac.uk/id/eprint/438050
ISSN: 0277-5387
PURE UUID: 2f33d130-438f-4503-9d15-eeb73cbff08a
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Date deposited: 26 Feb 2020 17:31
Last modified: 17 Mar 2024 05:20
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Contributors
Author:
Sarah J. Fieldhouse
Author:
Wim Klooster
Author:
Anthony M.J. Lees
Author:
Andrew W.G. Platt
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