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Original Articles

POLYCYCLES AND CAGES IN MOLECULAR ALUMO-POLYSILOXANES—(Ph2SiO)8[Al(O)OH]4 Used as a Supramolecular Target and “Auto-Condensation” Within the Molecule

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Pages 651-660 | Published online: 12 Aug 2010
 

Abstract

In this preliminary review the reaction of [Ph2SiO]8[AlO(OH)]4 toward 1,3-diaminopropane and hexamethyldisilazane is discussed in view of supramolecular chemistry and access to structural transformations of the original polycycle. Two distinct adducts may be isolated in the first case: [Ph2SiO]8[AlO(OH)]4· 3H2N-CH2CH2CH2-NH2 and [Ph2SiO]8[AlO(OH)]4· 2H2N-CH2CH2CH2-NH2. Whereas in the 1:3 adduct the four protic hydrogen atoms of the inner Al4(OH)4 ring are involved in O…H…N hydrogen bridges to two terminal diaminopropanes and a bridging diaminopropane thus forming an O…H…N(H)2-CH2CH2CH2N(H)2 …H…O loop, in the 1:2 adduct two such O…H…N(H)2-CH2CH2CH2N(H)2…H…O loops are present. When [Ph2SiO]8[AlO(OH)]4 is allowed to react with hexamethyldisilazane, again two different products may be obtained depending on the solvent: [Ph2SiO]8[AlO2]2[AlOO-SiMe3]2[NH4· THF]2 or [Ph2SiO]8[AlOO0.5]4· 2 py. This last reaction may be viewed as an inner condensation within [Ph2SiO]8[AlO(OH)]4 loosing two equivalents of water. Both products of the reaction with hexamethyldisilazane have an inner Al2O2 four-membered cycle in common, to which Al2O4Si2 eight-membered cycles are partly fused.

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