304854-91-9Relevant articles and documents
Chirale gallium- und indium-alkoxometallate
Pauls, Jochen,Chitsaz, Soheila,Neumueller, Bernhard
, p. 2028 - 2034 (2000)
Li2(S)-BINOLate ((S)-BINOL = (S)-(-)-2,2′-Dihydroxy-1,1′-binaphthyl) generated by dilithiation of (S)-BINOL with two equivalents nBuLi was reacted with GaCl3 und InCl3 in THF to the alkoxometalates [{Li(THF)2}-{Li(THF)}3(Ga((S)-BINOLate)3}] (1) and [{Li(THF)2}2-{Li(THF)}{In((S)-BINOLate)3}] · [{Li(THF)2J{Li(THF)}2(In((S)-BINOLate)3}] 2 (3), respectively. 1 and 3 crystallize from THF/toluene mixtures as · 2 toluene and 3 · 8 toluene. The treatment of PhCH2GaCl2 with Li2(S)-BINOLate in THF under reflux, followed by recrystallization of the product from DME gives the gallate [{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 group 13 metal was formed, built-up by three BINOLate ligands. The three Li+ counter ions act as bridging units by metal-oxygen coordination. The coordination sphere of the Li+ ions was completed, depending on the available space, by one or two THF ligands (1 · 2 toluene, 3 · 8 toluene) and one DME ligand (2 · 1.5 THF), respectively. The sterical dominance of the BINOLate ligands 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°.
