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

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Description/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.

Item Type: Article
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Keywords: lanthanides, phosphine oxides, crystal structures, nitrate complexes, yttrium, shifts, ions
Subjects: Q Science > QD Chemistry
Divisions: University Structure - Pre August 2011 > School of Chemistry
ePrint ID: 20215
Date Deposited: 21 Feb 2006
Last Modified: 27 Mar 2014 18:09
URI: http://eprints.soton.ac.uk/id/eprint/20215

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