X-Ray Structural Studies of Small-Bite Ligands on Large Cations – Lanthanide(III) Ions and Dimethylphosphate

Abstract

Reactions of lanthanide chlorides or trifluoracetates (tfa) or picrates with trimethylphosphate alone in the first two cases or trimethylphosphate plus 1,10-phenanthroline or 2,2′;6′,2′′-terpyridine in the third, result in the formation of crystalline products containing dimethylphosphate (dmp–). Single crystal X-ray structural characterisation of these materials has shown that the stoichiometrically simple Ln(dmp)3 species obtained with chloride reactants and the lighter lanthanides are polymeric and commonly dimorphic, while the stoichiometrically more variable mixed dmp/tfa complexes have structures closely related to one phase of the Ln(dmp)3 family, and the presence of picrate and aza-aromatic ligands enables the isolation of Y and Lu derivatives containing binuclear species. In all, the dmp– ligands adopt exclusively the κ1O;κ1O′ bridging mode, the overall results indicating that this should apply to the complete lanthanide series.