Bridging Titanium Nitrido Complexes Containing A Linear Ti-N-Ti Core with A Two-Coordinate Nitrido Ligand

A series of titanium mu 2-nitrido complexes supported by the triamidoamine ligand Xy-N3N (Xy-N3N={(3,5-Me2C6H3)NCH2CH2}3N3-) is reported. The titanium azido complex [(Xy-N3N)TiN3] (1-N3), prepared by salt metathesis of the chloride complex [(Xy-N3N)TiCl] (1-Cl) with NaN3, reacted with lithium metal or with alkali metal naphthalenides (alkali metal M=Na, K, and Rb) in THF to give the corresponding dinuclear mu 2-nitrido complexes M[(Xy-N3N)Ti=N-Ti(Xy-N3N)] (2-M; M=Li, Na, K, Rb). Single crystal X-ray diffraction studies of 2-Li, 2-Na, and 2-K revealed alkali metal dependent structures in the solid state. While 2-Li and 2-K contain a mu 2-nitrido ligand with a linear Ti-N-Ti core, 2-Na includes a mu 3-nitrido ligand as part of a T-shape Ti2NaN fragment with the sodium cation weekly coordinated to the nitrido nitrogen atom. When the synthesis of the nitrido complexes was carried out in the presence of excess alkali metals, decomposition of the nitrido complexes was observed affording some intractable titanium species along with the trialkali metal salts [M3(Xy-N3N)] (3-M) (M=Li, Na, K, and Rb). These salts were also prepared by deprotonation of (Xy-N3N)H3 with the corresponding alkali metal hexamethyldisilazide and characterized by multinuclear NMR spectroscopy as well as single crystal X-ray diffraction. A series of titanium mu 2-nitrido complexes supported by the triamidoamine ligand Xy-N3N (Xy-N3N={(3,5-Me2C6H3)NCH2CH2}3N3-) is reported. The titanium azido complex [(Xy-N3N)TiN3] (1-N3) reacted with lithium metal or with alkali metal naphthalenides (alkali metal M=Na, K, and Rb) in THF to give the corresponding dinuclear mu 2-nitrido complexes M[(Xy-N3N)Ti=N-Ti(Xy-N3N)] (2-M; M=Li, Na, K, Rb). While 2-Li and 2-K consist of a mu 2-nitrido ligand with a linear Ti-N-Ti core, 2-Na contains a T-shape mu 3-nitrido ligand with the sodium cation interacting with the aryl substituent. image