Titanium(III) complexes containing unprecedented (NH2BH2NHBH3) 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 -C5Me5) with NH3BH3 (3 equiv) at room temperature gives the paramagnetic dinuclear complex [{TiCp*(NH2BH3)}2(µ-NH2BH2NHBH3)], which at 80 ºC 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-NMe2BH2)] have been studied by X