Syntheses and Crystal Structures of Mononuclear and Binuclear Lanthanide Halide Complexes with Diglyme

Abstract

AbstractTwo types of isostructural complexes of lanthanide chlorides with diglyme have been synthesized. These are mononuclear molecular complexes [LnCl3(diglyme)(THF)] (Ln = Eu (1), Gd (2), Dy (3), Er (4), Yb (5); diglyme = diethylen glycol dimethyl ether) and binuclear molecular complexes [LnCl3(diglyme)]2 (Ln = Dy (3d), Er (4d), Yb (5d)). Complex 1 was obtained by the reaction of [EuCl3(DME)2] with diglyme in THF. The complexes 2–5 and 3d–5d resulted from reactions of LnCl3·6H2O, (CH3)3SiCl and diglyme in THF. The mononuclear complexes 2–5 crystallized directly from the solutions where the reactions of lanthanide compounds with diglyme took place. Recrystallizations of the powder products of the same reactions from dichloromethane resulted in the binuclear complexes 3d–5d. Reactions of lanthanide bromide hydrates, (CH3)3SiBr and diglyme in THF achieved mononuclear molecular complexes [LnBr3(diglyme)(L)] (Ln = Gd, L = H2O (6); Ln = Ho, L = THF (7)). Crystals of 6 and 7 were grown by recrystallization from dichloromethane. The lanthanide atoms (Ln = Eu–Yb) are seven‐coordinated in a distorted pentagonal bipyramidal fashion in all reported complexes, 1–7 and 3d–5d. Four oxygen atoms and three halide ions are coordinated to lanthanide atoms in 1–7, [LnX3(diglyme)(L)]. Four chloride ions, two bridging and two nonbridging, and three oxygen atoms are coordinated to lanthanide atoms in 3d–5d, [LnCl3(diglyme)]2.