Barium Bis(dimethylsilyl)amide – Adduct vs. Oxo Formation

Silylamide [Ba{N(SiHMe 2 ) 2 } 2 ] n reacts with 1,10‐phenanthroline (Phen) in toluene to give the donor adduct [Ba{N(SiHMe 2 ) 2 } 2 (Phen)] 2 . X‐ray structure analysis revealed a dimeric solid‐state structure with two bridging silylamido ligands and Ba ··· SiH β‐agostic interactions, which are most pronounced for the terminal silylamido ligands. Treatment of [Ba{N(SiHMe 2 ) 2 } 2 ] n with GaMe 3 did not lead to the isolation of putative Lewis acid adduct [Ba(μ‐{N(SiHMe 2 ) 2 })(μ‐Me)(GaMe 2 )] but resulted in the soluble, low aggregated barium oxo complex [Ba(μ 4 ‐O)(GaMe 3 ) 2 (toluene)] 2 , which is reminiscent of inverse crown ethers.