Co-complexation of lithium gallates on the titanium molecular oxide {[Ti(η5-C5Me5)(μ-O)}3(μ3-CH)]

Amide and lithium aryloxide gallates [Li(+){RGaPh(3)}(-)] (R = NMe(2), O-2,6-Me(2)C(6)H(3)) react with the μ(3)-alkylidyne oxoderivative ligand [{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)] (1) to afford the gallium-lithium-titanium cubane complexes [{Ph(3)Ga(μ-R)Li}{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)] [R = NMe(2) (3), O-2,6-Me(2)C(6)H(3) (4)]. The same complexes can be obtained by treatment of the [Ph(3)Ga(μ(3)-O)(3){Ti(η(5)-C(5)Me(5))}(3)(μ(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{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)](+) together with the anionic [(GaPh(3))(2)(μ-NMe(2))](-) unit. On the other hand, the reaction of 1 with Li(p-MeC(6)H(4)) and GaPh(3) leads to the complex [Li{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)][GaLi(p-MeC(6)H(4))(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{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)][PhLi(μ-C(6)H(5))(2)Ga(p-MeC(6)H(4))Ph] 6a.