H 2 O‐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 Me 3 SiBr in situ formed from commercially available disilane Si 2 Me 6 and Br 2 . This practical route allows to obtain the target lanthanum tribromide solvates [LaBr 3 (thf) 4 ] ( 1a ) and [LaBr 3 (dme) 2 ] 2 ( 1b ) as well as analogous early lanthanide molecular tribromide solvates [NdBr 3 (thf) 4 ] ( 2a ), [NdBr 3 (dme) 2 ] ( 2b ), [SmBr 3 (thf) 2 ] ( 3a ), and [SmBr 3 (dme) 2 ] ( 3b ) difficult to prepare by other solution‐based procedures. The molecular structure of 1b· 2CH 2 Cl 2 was determined by an XRD study.