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DOI: 10.1039/A807727D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2189-2196

Complexes of the lanthanide metals (La–Nd, Sm–Lu) with hypophosphite and phosphite ligands: crystal structures of [Ce(H2PO2)3(H2O)], [Dy(H2PO2)3] and [Pr(H2PO2)(HPO3)(H2O)]·H2O

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Joanne A. Seddon, Andrew R. W. Jackson, Roman A. Kresiński and Andrew W. G. Platt

Abstract

Reactions of lanthanide chlorides LnCl3 with NaH2PO2 in aqueous solution afforded a series of complexes [Ln(H2PO2)3(H2O)n] (Ln = La–Tb, n = 1; Ce–Nd, Dy–Lu; n = 0) with members falling into at least four separate structural types. The crystal structures of members of two of these types, [Ce(H2PO2)3(H2O)] and [Dy(H2PO2)3], have been determined for the first time, along with that of [Pr(H2PO2)(HPO3)(H2O)]·H2O, one of a new series of complexes [Ln(H2PO2)(HPO3)(H2O)n]·nH2O (Ln = La–Gd, n = 1; Tb–Lu; n = 0) obtained by controlled oxidation of [Ln(H2PO2)3(H2O)n]. The hydrated members of this series are notable due to their incorporation of chiral channels inhabited by water molecules, and to their ability reversibly to dehydrate. Steric angle sum calculations have been used to rationalise the morphologies of the new complexes.

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