Co-complexation of Lithium Gallates on the Titanium Molecular Oxide {[Ti(η5-C5Me5)(μ-O)}3(μ3-CH)]

Amide and lithium aryloxide gallates [Li+{RGaPh3}(-)] (R = NMe2, O-2,6-Me2C6H3) react with the mu(3)-alkylidyne oxoderivative ligand [{Ti(eta(5)-C5Me5)(mu-O)}(3)(mu(3)-CH)] (1) to afford the gallium-lithium-titanium cubane complexes [{Ph3Ga(mu-R)Li}{Ti(eta(5)-C5Me5)(mu-O)}(3)(mu(3)-CH)] [R = NMe2 (3), O-2,6-Me2C6H3 (4)]. The same complexes can be obtained by treatment of the [Ph3Ga(mu(3)-O)(3){Ti(eta(5)-C5Me5)}(3)(mu(3)-CH)] (2) adduct with the corresponding lithium amide or aryloxide, respectively. Complex 3 evolves with formation of 5 as a solvent-separated ion pair constituted by the lithium dicubane cationic species [Li{(mu(3)-O)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-CH)}(2)](+) together with the anionic [(GaPh3)(2)(mu-NMe2)](-) unit. On the other hand, the reaction of 1 with Li(p-MeC6H4) and GaPh3 leads to the complex [Li{(mu(3)-O)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-CH)}(2)][GaLi(p-MeC6H4)(2)Ph-3] (6). X-ray diffraction studies were performed on 1, 2, 4, and 5, while trials to obtain crystals of 6 led to characterization of [Li{(mu(3)-O)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-CH)}(2)][PhLi(mu-C6H5)(2)Ga(p-MeC6H4)Ph] 6a.