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Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide

Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide
Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide
The reaction of Ph3PO with LnCl(3) . nH(2)O (Ln=La-Lunot equalPm) in a 3.5:1 ratio in acetone produces [LnCl(3)(Ph3PO)(3)], whilst from a 6:1 ratio in ethanol the products are [LnCl(2)(Ph3PO)(4)]Cl . n(solvate). In the presence of [NH4][PF6] in ethanol solution, [LnCl(2)(Ph3PO)(4)]PF6 can be isolated. The last complexes are stable in solution but the [LnCl(3)(Ph3PO)(3)] and [LnCl(2)(Ph3PO)(4)]Cl partially interconvert in non-coordinating solvents, the neutral species being preferred by the lighter lanthanides, the cationic tetrakis complexes becoming more favoured towards the end of the series. The complexes have been characterised in the solid state by analysis and IR spectroscopy and in solution by P-31{H-1} NMR spectroscopy and conductance measurements. The crystal structures of trans-[LnCl(2)(Ph3PO)(4)]Cl.nEtOH (Ln=Tb or Yb) and mer-[LnCl(3)(Ph3PO)(3)].0.5Me(2)CO (Ln=La or Cc) are reported and discussed.
lanthanides, phosphine oxides, crystal structures, nitrate complexes, yttrium, shifts, ions
0020-1693
1083-1091
Glazier, Mikael J.
4073d5b9-ea54-4490-af54-70b7ea02e139
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Matthews, Melissa L.
48114504-dd8b-4879-b428-f31fada714e7
Thornton, Pamela L.
3f96f6c2-1ce2-44ae-8ee2-808db1de02b1
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Glazier, Mikael J.
4073d5b9-ea54-4490-af54-70b7ea02e139
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Matthews, Melissa L.
48114504-dd8b-4879-b428-f31fada714e7
Thornton, Pamela L.
3f96f6c2-1ce2-44ae-8ee2-808db1de02b1
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Glazier, Mikael J., Levason, William, Matthews, Melissa L., Thornton, Pamela L. and Webster, Michael (2004) Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide. Inorganica Chimica Acta, 357 (4), 1083-1091. (doi:10.1016/j.ica.2003.09.015).

Record type: Article

Abstract

The reaction of Ph3PO with LnCl(3) . nH(2)O (Ln=La-Lunot equalPm) in a 3.5:1 ratio in acetone produces [LnCl(3)(Ph3PO)(3)], whilst from a 6:1 ratio in ethanol the products are [LnCl(2)(Ph3PO)(4)]Cl . n(solvate). In the presence of [NH4][PF6] in ethanol solution, [LnCl(2)(Ph3PO)(4)]PF6 can be isolated. The last complexes are stable in solution but the [LnCl(3)(Ph3PO)(3)] and [LnCl(2)(Ph3PO)(4)]Cl partially interconvert in non-coordinating solvents, the neutral species being preferred by the lighter lanthanides, the cationic tetrakis complexes becoming more favoured towards the end of the series. The complexes have been characterised in the solid state by analysis and IR spectroscopy and in solution by P-31{H-1} NMR spectroscopy and conductance measurements. The crystal structures of trans-[LnCl(2)(Ph3PO)(4)]Cl.nEtOH (Ln=Tb or Yb) and mer-[LnCl(3)(Ph3PO)(3)].0.5Me(2)CO (Ln=La or Cc) are reported and discussed.

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More information

Published date: 10 March 2004
Keywords: lanthanides, phosphine oxides, crystal structures, nitrate complexes, yttrium, shifts, ions

Identifiers

Local EPrints ID: 20215
URI: http://eprints.soton.ac.uk/id/eprint/20215
ISSN: 0020-1693
PURE UUID: 003f84bf-973e-40e2-87c3-cba3f46edb78
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971

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Date deposited: 21 Feb 2006
Last modified: 16 Mar 2024 02:35

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Contributors

Author: Mikael J. Glazier
Author: William Levason ORCID iD
Author: Melissa L. Matthews
Author: Pamela L. Thornton
Author: Michael Webster

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