Synthesis and structure of cyclic aluminum disiloxides

C. Krempner, H. Reinke, K. Weichert

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The synthesis and structure of cyclic five- and six-membered aluminum disiloxides containing the chelating diolate ligands SiMe2[(Me 3Si)2SiO]22- (1a)-2H, [(Me 3Si)2SiO]22- (1b)-2H, and [Me(Me3Si)3SiSiO]22- (rac-1c)-2H are reported. The dinuclear aluminum disiloxides [SiMe2{(Me 3Si)2SiO}2AlMe]2 (2a) and [(E)-{Me(Me3Si)3SiSiO}2AlMe]2 (2c) were prepared in n-pentane by treatment of AlMe3 with 1 equiv of the free ligands la and 1a, respectively. The analogous reaction of le with AlMe3 in THF as solvent yielded the monomeric THF adduct (E)-[Me(Me3Si)3SiSiO]2AlMe·THF (4c). Irrespective of the molar ratio, treatment of 1b with AlMe3 in pentane gave the trinuclear complex [{(Me3Si)2SiO} 2]2Al3Me5 (3b) as the major product, whereas the thermally stable AlMe3 adduct (E)-[Me(Me Si)3SiSiO]2AlMe·AlMe3 (5c) was synthesized by employing a 2-fold excess of AlMe3 in the reaction with 1c. Treatment of 4c with B(C6F5)3 led to full exchange of the methyl group by C6F5 with quantitative formation of (E)-[Me-(Me3Si)3SiSiO] 2Al(C6F5)·THF (6c) and a mixture of B(C6F5)3-nMen, where n = 1, 2, 3. The reaction of 4c with phenol did not yield the expected complex (E)-[Me(Me3Si)3SiSiO]2AlOPh·THF; rather, quantitative ligand transfer to give the spirocyclic complex {[(E)-{Me(Me 3Si)3SiSiO}2]2Al}-H + (7c) occurred. The structures of the complexes 2a, 2c, 3b, 4c, and 7c were determined by X-ray crystallography.

Original languageEnglish
Pages (from-to)1386-1392
Number of pages7
Issue number6
StatePublished - Mar 12 2007


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