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Inner and Outer Sphere Coordination of Tricyclohexylphosphine oxide with Lanthanide Bromides

LEES, Anthony M, bowden, Allen and platt, Andy (2015) Inner and Outer Sphere Coordination of Tricyclohexylphosphine oxide with Lanthanide Bromides. Polyhedron, 91. pp. 110-119.

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Abstract or description

Complexes of lanthanide bromides with tricyclohexylphosphine oxide (Cy3PO) form three distinct structural classes. Type I complexes LnBr3(Cy3PO)3 have been structurally characterised for Ln = La, Pr, Nd, Gd and Ho and are molecular 6 coordinate with a distorted meridional octahedral arrangement. Type II complexes are based on pentagonal bipyramidal [Ln(Cy3PO)n(H2O)5]3+ structures and fall into three subsets; n = 2 and 3 have been isolated for Ln = Lu and n = 4 with Ln = La, Dy, Er and Yb. The structures of [Lu(Cy3PO)2(H2O)5]Br3•2EtOH and [Ln(Cy3PO)2(H2O)5]Br3 (Ln = Dy, Er, Yb) have been determined. When n = 2 both ligands are directly coordinated to the metal whilst complexes in which n = 4 have two ligands bonded to the metal and two hydrogen bonded to the coordinated water molecules. Analysis of the bond distances shows that the lanthanide contraction accounts for about 99% of the observed trends. The infrared spectra of the complexes give a good means of identifying the structural types produced. 31P NMR show that the Type I complexes are fluxional in solution and that the Type II complexes undergo ligand exchange between metal and H-bonded ligands. Analysis of the lanthanide induced shifts indicates that the Type II complexes are isostructural in solution.

Item Type: Article
Subjects: F100 Chemistry
Faculty: Previous Faculty of Computing, Engineering and Sciences > Sciences
Depositing User: Andy PLATT
Date Deposited: 14 May 2015 11:11
Last Modified: 01 Jun 2017 01:38

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