Impact of Group 13 Metals on Cp2TiCl2 Reduction and Structural Characterization of Resulting Compounds

The aim of the current study was to examine the effects of group 13 metals on Cp2TiCl2 reduction in the presence of 2-methoxy­ethanol (MeO­Et­OH) or ethanol (EtOH) and the compositions of the resulting products. Direct reaction of Cp2TiCl2 and M [Al, Al (Fe contaminated), Ga, In] in toluene/​alcohol for 2 h gave a new family of uncommon homo- and heterometallic compounds: [Cp2­Ti2Al­(μ,η2-OEt­OMe)4­Cl2]­[Ti2­(μ,η2-OEt­OMe)3­(η2-OEt­OMe)2­Cl4] (1), [Cp2­Ti2Al­(μ,η2-OEt­OMe)4­Cl2]Cl (2), [Cp2­Ti2Al­(μ,η2-OEt­OMe)4­Cl2]­[Cp2Ti­(η2-HOEt­OMe)]­[FeCl4] (3), [Cp2Ti­(η2-HOEt­OMe)]­[Ga2Cl6]0.25­[Cl]0.5 (4), [Cp3Ti2­(μ-OEt)2­(OEt)]­[GaCl4] (5), [CpTi­(μ,η2-OEt­OMe)­Cl]2 (6), and [Cp3Ti2­(μ,η2-OEt­OMe)­(μ-OEt­OMe)­Cl] (7). The reaction with indium for 48 h resulted in isolation of [TiIn2­(μ,η2-OEt­OMe)4­(OEt­OMe)2­Cl4] (8), [In2­(μ-OEt­OMe)2­(HOEt­OMe)4­Cl4]2 (9), and [Ti­(OEt­OMe)4] (10). The complexes were characterized using elemental analysis, IR and NMR spectroscopies, and, for 1–9, single-crystal X-ray diffraction. The use of metallic gallium and indium to reduce Cp2­TiCl2 opens up a previously unexplored path that may provide access to novel and unique compounds.