Adduct formation and dealkylsilylation reactions of alumazene
| Authors | |
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| Year of publication | 2005 |
| Type | Article in Proceedings |
| Conference | Pacifichem 2005 - INOR 166 |
| MU Faculty or unit | |
| Citation | |
| Field | Inorganic chemistry |
| Keywords | iminoalane; alumazene; dealkylsilylation |
| Description | Trimeric iminoalane alumazene, [2,6-(i-Pr)2C6H3NAlMe]3, possesses a central six-membered Al3N3 planar ring. Its high reactivity is caused by a polarity of the Al-N bonds and a small delocalization of the ŕ electrons in the ring. We will present the results of our studies on the reactivity of alumazene with a variety of oxygen and nitrogen bases and trimethylsilyl esters of acids of phosphorus and sulfur with the aim of obtaining new polycyclic and polyhedral molecules. Trimethylester of phosphoric acid in the reaction with alumazene at room temperature forms a cis-adducts A and on heating affords intractable mixtures of products. On the other hand, mono- and bisadduct of triphenylphosphine oxide were structurally characterized and a trans isomer B was revealed by X-ray diffraction analysis. Dealkylsilylation reactions of trimethylsilyl esters of phosphonic acids (RP(O)(OSiMe3)2, R = Me, Ph, CCl3) lead to bicyclic products C or D, depending on the size of R. Phosphoric acid ester, OP(OSiMe3)3, provided a heteroadamantane compound E. Analogous dealkylsilylation reaction was observed with trimethylsilyl esters of sulfonic acids and provided bicyclic moieties similar to C that assemble into a hexameric supramolecular ring in the solid state. The reactions of pyridines and nitriles (RCN, R = Me3Si, i-Pr, 4-MeOC6H4, 4-MeC6H4, 2,6-F2C6H3) with alumazene were studied in analogy to their reactions with AlMe3. Mono-, bis- and tris-adducts were observed spectroscopically and also were structurally characterized. The cis- and trans isomers were observed for the bis-adducts of 2,6-X2C6H3CN (X = F, Cl) and MeC6H4CN, respectively. |
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