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Monoglyme forms a molecular 1:1 adduct with AlBr 3  which dissociates into the ions AlBr 2 (DME) 2  +  and AlBr 4  -  in DME, CH 2 Br 2  and CDCl 3  as solvents. A hexacoordinated Al center is present in the solid adduct AlBr 3 ·diglyme. The oxygen and bromine atoms are arranged in a meriodional configuration as shown by X-ray crystallography. However, in solution dissociation occurs into AlBr 2 (diglym) 2  +  and AlBr 4  - . Not unexpectedly, AlBr 3  forms the adduct AlBr 3 ·2THF with tetrahydrofuran. The dioxane adduct AlBr 3 ·diox is polymeric in the solid state and has a chain structure with pentacoordinated trigonal-bipyramidal Al centers. The Br atoms are arranged in a slightly distorted trigonal plane. In solution, the presence of tetracoordinated Al is indicated by  27 AI NMR spectroscopy. AlBr 3  cleaves one of the C-O bonds of 12-crown-4 leading to the dimer of ω-bromo-tetra(ethyleneoxy)aluminium dibromide. This dimer contains pentacoordinated Al centers as proven by X-ray structure analysis. In contrast, the adduct of AlBr 3  with 15-crown-5 is most likely an ionic compound, and is best described as [AlBr 2 (15-crown-5)]AlBr 4  based on  27 Al NMR and IR data.

zeitschrift für naturforschung b

Über einige Aluminiumbromid-Ether-Addukte: Strukturen in Lösung und im festen Zustand / Aluminium Bromide Ether Adducts: Structures in Solution and in the Solid State