Complexes of lanthanide nitrates with tri-isopropylphosphine oxide

Bowden, Allen, Coles, Simon J., Pitak, Mateusz B. and Platt, Andrew W.G. (2014) Complexes of lanthanide nitrates with tri-isopropylphosphine oxide. Polyhedron, 68, 258-264. (doi:10.1016/j.poly.2013.10.028).

Abstract

The complexes formed on reaction of tri-isopropylphosphine oxide ((C3H7)(3)PO = (Pr3PO)-Pr-i = L) and lanthanide nitrates have been studied. The new compounds have been characterised by elemental analysis, infrared and P-31 NMR spectroscopy in CD2Cl2 solution. On reaction of lanthanide nitrates and L in 1:3 ratios, well defined Ln(NO3)(3)L-3 are obtained for Ln = La-Eu with complexes for the heavier lanthanides forming mixtures of Ln(NO3)(3)L-3 and Ln(NO3)(3)L-2. Analytically pure complexes Ln(NO3)(3)L-2 can be isolated for Yb and Lu. Single crystal X-ray structures for Ln(NO3)(3)L-3, Ln = La (1), Ce (2), Pr (3), the ionic complex [Er(NO3)(2)L-3(H2O)][NO3] (4) and Ln(NO3)(3)L-2, Ln = Yb (5), Lu (6) are reported. The P-31 solution NMR spectra of Ln(NO3)(3)L-3 show that the complexes are fluxional at ambient temperature with spectra consistent with static structures observed at lower temperatures for some complexes. The structures and solution properties are discussed in terms of the steric and electronic properties of the ligand.

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Contributors

Author: Simon J. Coles

Author: Mateusz B. Pitak

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