Chiral gallium and indium alkoxometalates

Li-2(S)-BINOLate ((S)-BINOL = (S)-(-)-2,2'-Dihydroxy-1,1'-binaphthyl) gener ated by dilithiation of (S)-BINOL with two equivalents (BuLi)-Bu-n was reac ted with GaCl3 und InCl3 in THF to the alkoxometalates [{Li(THF)(2)}{Li(THF )}(2){Ga((S)-BINOLate)(3)}] (1) and [{Li(THF)(2)}(2){Li(THF)}{In((S)-BINola te)(3))] . [{Li(THF)(2)}{Li(THF)}(2){In((S)-BINOLate)(3)}](2) (3), respecti vely. 1 and 3 crystallize from THF/toluene mixtures as 1 . 2 toluene and 3 . 8 toluene. The treatment of PhCH2GaCl2 with Li-2(S)-BINOLate in THF under reflux, followed by recrystallization of the product from DME gives the ga llate [{Li(DME)}(3){Ga((S)-BINOLate)(3)}] . 1.5 THF (2 . 1.5 THF). 1-3 were characterized by NMR, IR and MS techniques. In addition, 1 . 2 toluene, 2 . 1.5 THF and 3 . 8 toluene were investigated by X-ray structure analyses. According to them, a distorted octahedral coordination sphere around the gr oup 13 metal was formed, built-up by three BINOLate ligands. The three Licounter ions act as bridging units by metal-oxygen coordination. The coordi nation sphere of the Li+ ions was completed, depending on the available spa ce, by one or two THF ligands (1 . 2 toluene, 3 . 8 toluene) and one DME li gand (2 . 1.5 THF), respectively. The sterical dominance of the BINOLate li gands can be shown by the almost square-planar coordination of the Li+ ions in 2 . 1.5 THF giving a small twisting angle of only 17 degrees.