Rhodium/iridium-titanium azaheterometallocubanes

Treatment of [[Ti(eta (5)-C5Me5)(mu- NH)](3)(mu (3)-NH)] (1) with the diole fin complexes [{MCl(cod)}(2)] (M = Rh, Ir; cod = 1,5-cyclooctadiene) in tol uene afforded the ionic complexes [M(cod) (mu (3)-NH)(3)Ti-3(eta (5)-C5Me5) (3)(mu (3)-N)]Cl[M = Rh (2), Ir (3)]. Reaction of complexes 2 and 3 with [A g(BPh4)] in dichloromethane leads to anion metathesis and formation of the analogous ionic derivatives [M(cod)(mu (3)-NH)(3)Ti-3-(eta (5)-C5Me5)(3)(mu (3)-N)][BPh4] [M = Rh (4), Ir (5)]. An X-ray crystal structure determinati on for 5 reveals a cube-type core [IrTi3N4] for the cationic fragment, in w hich 1 coordinates in a tripodal fashion to the iridium atom. Reaction of t he diolefin complexes [{MCl(cod)}(2)] (M = Rh, Ir) and [{RhCl(C2H4)(2)}(2)] with the lithium derivative [{Li(mu (3)-NH)(2)(mu (3)-N)-Ti-3(eta (5)-C5Me 5)(3) (mu (3)-N)}(2)].C7H8 (6 .C7H8) in toluene gave the neutral cube-type complexes [M(cod)(mu (3)-NH)(2)(mu (3)-N)Ti-3- (eta (5)-C5Me5)(3)(mu (3)-N) ] [M = Rh (7), Ir (8)] and [Rh(C2H4)(2)(mu (3)-NH)(2)(mu (3)-N)Ti-3(eta (5) -C5Me5)(3)(mu (3)-N)] (9), respectively. Density functional theory calculat ions have been carried out on the ionic and neutral azaheterometallocubane complexes to understand their electronic structures.