H2O‐Catalyzed Route to Early Lanthanide Tribromide THF and DME Solvates from Oxides

A convenient one‐pot synthetic protocol towards THF and DME solvates of lanthanum and other early lanthanide tribromides was developed using the water‐catalyzed reaction of lanthanide(III) oxides with highly reactive Me3SiBr in situ formed from commercially available disilane Si2Me6 and Br2. This practical route allows to obtain the target lanthanum tribromide solvates [LaBr3(thf)4] (1a) and [LaBr3(dme)2]2 (1b) as well as analogous early lanthanide molecular tribromide solvates [NdBr3(thf)4] (2a), [NdBr3(dme)2] (2b), [SmBr3(thf)2] (3a), and [SmBr3(dme)2] (3b) difficult to prepare by other solution‐based procedures. The molecular structure of 1b·2CH2Cl2 was determined by an XRD study.