Titanium alkali metal nitrido complexes.

Treatment of [(Ti(eta5-C5Me5)(mu-NH))3(mu3-N)] with alkali metal bis(trimethylsilyl)amido reagents in toluene afforded the complexes [M(mu3-N)(mu3-NH)2[Ti3(mu5-C5Me5)3(mu3-N)]]2 (M = Li (2), Na, (3), K (4)). The molecular structures of 2 and 3 have been determined by X-ray crystallographic studies and show two azaheterometallocubane cores [MTi3N4] linked by metal-nitrogen bonds. Reaction of the lithium derivative 2 with chlorotrimethylsilane or trimethyltin chloride in toluene gave the incomplete cube nitrido complexes [Ti3(eta5-C5Me5)3(mu-NH)2(mu-NMMe3)(mu3-N)] (M = Si (5), Sn (6)). A similar reaction with indium(I) or thallium(I) chlorides yielded cube-type derivatives [M(mu3-N)(mu3-NH)2[Ti(eta5-C5Me5)3(mu3-N)] (M=In (7), Tl (8)).