The reaction of GaMe 3 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 PhCH 2 InCl 2 with 1 equiv of Li 2 ((S)-BINOLate) in THF at reflux and recrystallization from DME led not to the desired organoindium alkoxide but to [{(DME)Li} 3 {In((S)-BINOLate) 3 }]‚2DME (2‚2DME). The similar salt [{(DME)Li} 3 {In((S)-BINOLate) 3 }]‚0.75THF (2‚0.75THF) was obtained by direct synthesis of InCl 3 with 3 equiv of Li 2 ((S)-BINOLate) in THF at 65 °C and recrystallization from DME. The compounds 1 and 2 are 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 InCl 3 with 3 equiv of K 2 ((S)-BINOLate) in toluene, is very 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 1 is dimeric with a Ga 2 O 2 four-membered ring. 2 consists of a tetranuclear InO 6 Li 3 skeleton in which every Li + ion is coordinated by one additional DME ligand. The basic structural motif in 3, an InO 6 K 3 core, is comparable to the skeleton in 2. However, the coordinated toluene molecules of every K + ion in 3 are bound by mainly electrostatic metal-π-electron interactions.BINOLate complexes of a variety of metals are very valuable and effective catalysts and reagents for enantioselective synthesis. [1][2][3][4][5][6] Important for the understanding of the respective mechanism is a knowledge of the structure of the BINOLate-metal complexes. Therefore, a number of structural investigations were performed, for example, with Al 1 , Ga, In, 7 Ln, 5 Cr, and Fe. 8 For all of these complexes tetrahedral or octahedral coordination of the central metal was found. For some metals both types are known. It is worth mentioning that at least one coordination site at the central metal should be vacant for a successful enantioselective reaction. 1 However, there are examples as in the enantioselective transfer of MeLi to aldehydes in the presence of [{-(THF) 2 Li} 3 {Ln(BINOLate) 3 }] 5 where the Ln center pos-sesses coordination number 6. So it is not clear whether the coordination number 4 of the central metal is essential or not.We report here a new organometallic gallium-BINO-Late species and three tetranuclear complexes with M 3 O 6 In cores (M ) Li, K), and we focus on the synthesis and structures of the compounds, not on the application in organic synthesis. Experimental SectionGeneral Procedures. All experiments were carried out under an atmosphere of argon using Schlenk techniques. Purification and drying of the solvents were performed using standard methods. 9 GaMe3 was donated by the group of Prof. Dr. J. Lorberth. (S)-(-)-BINOL was purchased from Merck-Schuchardt. PhCH2InCl2 was prepared according to literature procedures. 10 Solvent-free Li2((S)-BINOLate) was prepared by treatment of BINOL ...

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