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

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), pp. 1083-1091. (doi:10.1016/j.ica.2003.09.015).

Record type: Article


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


Local EPrints ID: 20215
ISSN: 0020-1693
PURE UUID: 003f84bf-973e-40e2-87c3-cba3f46edb78
ORCID for William Levason: ORCID iD

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Date deposited: 21 Feb 2006
Last modified: 17 Jul 2017 16:29

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

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