Crystals, Vol. 13, Pages 877: Intramolecularly Stabilized o-Carboranyl Aluminum Complexes: Synthesis, Characterization, and X-ray Structural Studies

Crystals, Vol. 13, Pages 877: Intramolecularly Stabilized o-Carboranyl Aluminum Complexes: Synthesis, Characterization, and X-ray Structural Studies

Crystals doi: 10.3390/cryst13060877

Authors: Honglae Sohn Jong-Dae Lee

The chelating aluminum complex [2-(Me2NCH2)C2B10H10]AlX2 (X = Br 3, CH3 4) was synthesized using 2-dimethylaminomethyl-o-carboranyl lithium (LiCabN, 2) with aluminum tribromide (AlBr3) or dimethylaluminum bromide (Me2AlBr), resulting in a modest yield. Compound 4 was obtained by reacting compound 3 with methyllithium (CH3Li) in toluene. All compounds were characterized using infrared (IR) spectroscopy; 1H, 11B, 13C nuclear magnetic resonance (NMR) spectroscopy; and X-ray crystallography. X-ray structural studies of CabNAlBr2 (3) and CabNAlMe2 (4) (CabN = 2-dimethylaminomethyl-o-carboranyl) indicated that the aluminum atom was located at the center of a distorted tetrahedron. Crystal structures of CabNAlBr2 (3) [a = 8.9360(3) Å, b = 12.0358(9) Å, c = 14.7730(4) Å, α = β = γ = 90°] and CabNAlMe2 (4) [a = 8.9551(3) Å, b = 11.9126(9) Å, c = 14.7711(4) Å, α = β = γ = 90°] were obtained. The reactivity of aluminum complexes 3 and 4 with Lewis bases, such as H2O, pyridine, alkylamines, and arylamines, confirmed their rapid decomposition due to the strong Lewis acidity of aluminum metals.