Synthesis of anhydrous lanthanide chloride complexes from oxides and the crystal structure of [GdCl_3(thf)_2(tmeda)]

摘要

Complexes of [LnCl_3(dme)_2] (Ln = Sm, Gd; dme = dimethoxyethane) were prepared in dimethoxyethane solution from the lanthanide oxides and hydrogen chloride, which was formed in situ from chlorotrimethylsilane and water. The recrystallization of [LnCl(dme)_2] from tetrahydrofuran in the presence of tetramethylethylenediamine (tmeda) resulted in [LnCl_3(thf)_2(tmeda)] (Ln = Sm, Gd). The samarium and gadolinium complexes were found to be isomorphous by unit cell determination. Each seven-coordinated gadolinium atom adopts a distorted pentagonal bipyramidal geometry with chlorine atoms in axial positions. The thermal decomposition of the compounds in argon resulted in LnOCl.