Titanium alkali metal nitrido complexes

Treatment of [{Ti(eta (5)-C5Me5)(mu -NH)}(3)(mu (3)-N)] with alkali metal b is(trimethylsilyl)amido reagents in toluene afforded the complexes [M(mu (3 )-N)(mu (3)-NH)(2){Ti-3 (eta (5)-C5Me5)(3)(mu (3)-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 [MTi 3N4] linked by metal - nitrogen bonds. Reaction of the lithium derivative 2 with chlorotrimethylsilane or trimethyltin chloride in toluene gave the in complete cube nitrido complexes [Ti-3(eta (5)-C5Me5)(3)(mu -NH)(2)(mu- NMMe 3)(mu (3)-N)] (M=Si (5). Sn (6)). A similar reaction with indium(I) or thal lium(I) chlorides yielded cube-type derivatives [M(mu (3)-N)(mu (3)-NH)(2){ Ti(eta (5)-C5Me5)}(3)(mu (3)-N)] (M=In (7). T1 (8)).