BINOL compounds of group 13

The reaction of GaMe3 with. 1 equiv of (S)-BINOL ((S)-(-)-2,2'-dihydroxy-1, 1'-binaphthyl) in toluene at reflux conditions gave after recrystallization from THF the chiral organogallium alkoxide [(THF)MeGa((S)-BINOLate)](2) (1 ). In contrast treatment of PhCH2InCl2 with 1 equiv of Li-2((S)-BINOLate) i n THF at reflux and recrystallization from DME led not to the desired organ oindium alkoxide but to [{(DME)Li}(3){In((S)-BINOLate)3}].2DME (2.2DME). Th e similar salt [{(DME)Li}(3){In((S)-BINOLate)(3)}].0.75THF (2.0.75THF) was obtained by direct synthesis of InCl3 with 3 equiv of Li-2((S)-BINOLate) in THF at 65 degreesC and recrystallization from DME. The compounds 1 and 2 a re readily soluble only in donor solvents, while the potassium derivative [ {(toluene)(2)K}(3){In((S)-BINOLate)(3)}].2toluene (3.2toluene), obtained in the reaction of InCl3 with 3 equiv of K-2((S)-BINOLate) in toluene, is ver y soluble in toluene and n-hexane. 1-3 have been characterized by their NMR , IR, and MS spectra as well as by X-ray analyses. Compound I is dimeric wi th a Ga2O2 four-membered ring. 2 consists of a tetranuclear InO6Li3 skeleto n in which every Li+ ion is coordinated by one additional DME ligand. The b asic structural motif in 3, an InO6K3 core, is comparable to the skeleton i n 2. However, the, coordinated toluene molecules of every K+ ion in 3 are b ound by mainly electrostatic metal-pi -electron interactions.