Ammonia‐Borane Derived BN Fragments Trapped on Bi‐ and Trimetallic Titanium(III) Systems

Titanium(III) complexes containing unprecedented (NH 2 BH 2 NHBH 3 ) 2− and {N(BH 3 ) 3 } 3− ligands have been isolated, and their structures elucidated by a combination of experimental and theoretical methods. The treatment of the trimethyl derivative [TiCp*Me 3 ] (Cp*=η 5 ‐C 5 Me 5 ) with NH 3 BH 3 (3 equiv) at room temperature gives the paramagnetic dinuclear complex [{TiCp*(NH 2 BH 3 )} 2 (μ‐NH 2 BH 2 NHBH 3 )], which at 80 °C leads to the trinuclear hydride derivative [{TiCp*(μ‐H)} 3 {μ 3 ‐N(BH 3 ) 3 }]. The bonding modes of the anionic BN fragments in those complexes, as well as the dimethylaminoborane group trapped on the analogous trinuclear [{TiCp*(μ‐H)} 3 (μ 3 ‐H)(μ 3 ‐NMe 2 BH 2 )], have been studied by X‐ray crystallography and density functional theory (DFT) calculations.