Intramolecularly Base-Stabilized Group 13 Aryloxide Complexes

Three group 13 complexes of the ortho-chelating 2,4,6-tris((dimethylamino)methyl)phenoxy (ArⁿHD⁻) ligand have been prepared. Reaction of the lithio derivative, ArⁿOLi, with gallium trichloride in 1:1 stoichiometry afforded [ArⁿOGaCl₂]₂ (1). Treatment of gallium or indium trichloride with 2 equiv of ArⁿOLi resulted in the gallate and indate complexes [(ArⁿO)₂GaCl₂]Li (2) and [(ArⁿO)₂lnCl₂]Li (3), respectively. Compound 2 was also prepared by addition of 1 equiv of ArⁿHDLi to 1. The structure of the indate complex, 3, has been determined by X-ray crystallography. Compound 3 crystallizes in the monoclinic space group C2/c with a = 14.903(3) Å, b = 14.936-(3) Å, c = 22.076(4) A, β = 101.78(3)°, V = 4810(2) ų, and Z = 4. All three compounds were characterized on the basis of elemental analysis, NMR, and mass spectral data.