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 μ3-alkylidyne oxoderivative ligand [{Ti­(η5-C5Me5)­(μ-O)}3(μ3-CH)] (1) to afford the gallium–lithium–titanium cubane complexes [{Ph3Ga­(μ-R)­Li}­{Ti­(η5-C5Me5)­(μ-O)}3(μ3-CH)] [R = NMe2 (3), O-2,6-Me2C6H3 (4)]. The same complexes can be obtained by treatment of the [Ph3Ga­(μ3-O)3{Ti­(η5-C5Me5)}3(μ3-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{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CH)}2]+ together with the anionic [(GaPh3)2(μ-NMe2)]− unit. On the other hand, the reaction of 1 with Li­(p-MeC6H4) and GaPh3 leads to the complex [Li­{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CH)}2]­[GaLi­(p-MeC6H4)2Ph3] (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{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CH)}2]­[PhLi­(μ-C6H5)2Ga­(p-MeC6H4)­Ph] 6a.