Syntheses and Crystal Structures of Lanthanide Chloride Complexes with Diglyme

Reactions of [LnCl 3 (DME) 2 ] (Ln = Nd, Sm, Ho, Lu; DME = dimethoxyethane) and diglyme (diglyme = diethylen glycol dimethyl ether) in THF resulted in polymeric [LnCl 3 (diglyme)] n (Ln = Nd ( 1 ), Sm ( 2 )) or mononuclear complexes [LnCl 3 (diglyme)(THF)] (Ln = Ho ( 3 ), Lu ( 4 )). Neodymium and samarium atoms in 1 and 2 are eight‐coordinated by three oxygen atoms from diglyme, one terminal and four bridging chloride ions. Holmium and lutetium atoms in 3 and 4 are seven‐coordinated by three oxygen atoms from diglyme, three chloride ions and one oxygen atom from THF. [ErCl 3 (diglyme)(H 2 O)] ( 5 ) resulted from the reaction of ErCl 3 ·6H 2 O, (CH 3 ) 3 SiCl and diglyme in THF. The molecular structures of 3 , 4 and 5 are similar, with either a molecule of THF coordinated to the lanthanide atom in 3 and 4 or with a molecule of water coordinated in 5 .