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

Titanium(III) complexes containing unprecedented (NH2 BH2 NHBH3 )2- and {N(BH3 )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*Me3 ] (Cp*=η5 -C5 Me5 ) with NH3 BH3 (3 equiv) at room temperature gives the paramagnetic dinuclear complex [{TiCp*(NH2 BH3 )}2 (μ-NH2 BH2 NHBH3 )], which at 80 °C leads to the trinuclear hydride derivative [{TiCp*(μ-H)}3 {μ3 -N(BH3 )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 (μ3 -H)(μ3 -NMe2 BH2 )], have been studied by X-ray crystallography and density functional theory (DFT) calculations.