Binary and Halide-free Catalyst Systems Based on Al/Ga/In Aminopyridylbisphenolate Complexes for the Cycloaddition of Epoxides and CO.

Group 13 complexes bearing an aminopyridylbisphenol ligand have been prepared [; L = ligand, M = Al (X = Cl and Br), Ga (X = Cl, Br, and I), or In (X = Cl)]. The structures of the complexes containing the chloride ligand (; M = Al, Ga, and In) have been directly compared through an X-ray crystallography study, with differences in the monomeric or dimeric nature of their structures observed. All of the complexes obtained have been studied as potential catalysts for the synthesis of cyclic carbonates from epoxides and CO. It has been found that the indium complex, as part of a traditional binary catalyst system (catalyst + -butylammonium halide cocatalyst), displays the highest catalytic activity and is active under rather mild reaction conditions (balloon pressure of CO). Meanwhile, it has been found that the complex is a competent single-component catalyst (no need for addition of a cocatalyst) at more elevated reaction temperatures and pressures. A full substrate scope has been performed with both developed catalyst systems to demonstrate their applicability. In addition to the experimental results, a density functional theory study was performed on both catalyst systems. These results explain both why the indium catalyst is the most active under binary catalyst system conditions and how the gallium catalyst with an iodide () is able to act as a single-component catalyst in contrast to the indium-based complex.