Departamento de Química Inorgánica, Universidad de Alcalá, Campus Universitario, 28871 Alcalá de Henares, Madrid, Spain.
Inorg Chem. 2012 Aug 20;51(16):8964-72. doi: 10.1021/ic301057u. Epub 2012 Jul 30.
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.
酰胺和锂芳氧基镓酸盐 [Li(+){RGaPh(3)}(-)]（R = NMe(2), O-2,6-Me(2)C(6)H(3)）与 μ(3)-烷基idyne 氧衍生物配体 [{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)]（1）反应，生成镓-锂-钛立方烷配合物 [{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)]。通过分别用相应的锂酰胺或芳氧基处理 [Ph(3)Ga(μ(3)-O)(3){Ti(η(5)-C(5)Me(5))}(3)(μ(3)-CH)]（2）加成物，也可以得到相同的配合物。配合物 3 与形成 5 一起演变，5 是由锂双立方阳离子物种 Li{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)与阴离子 (GaPh(3))(2)(μ-NMe(2))单元组成的溶剂分离离子对。另一方面，1 与 Li(p-MeC(6)H(4))和 GaPh(3)的反应导致配合物 [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）的形成。对 1、2、4 和 5 进行了 X 射线衍射研究，而尝试获得 6 的晶体导致了 [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 的表征。
