An alkyl-substituted aluminium anion with strong basicity and nucleophilicity
| Autor: | Shuhei Takamori, Satoshi Kurumada, Makoto Yamashita |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry General Chemical Engineering Aluminate chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences Crystallography chemistry.chemical_compound Nucleophile chemistry Aluminium Electrophile Density functional theory Lewis acids and bases Lone pair Alkyl |
| Zdroj: | Nature Chemistry. 12:36-39 |
| ISSN: | 1755-4349 1755-4330 |
| DOI: | 10.1038/s41557-019-0365-z |
| Popis: | Aluminium anions with an unoccupied orbital are generally considered as highly difficult synthetic targets, as aluminium is the most electropositive element in the p block. Stabilizing effects from two nitrogen substituents and/or the coordination of a Lewis base were recently used to synthesize the first examples of anionic nucleophilic aluminium species. Here we show the synthesis and properties of a potassium salt of a non-stabilized dialkylaluminium anion that exhibits very strong basicity, which reflects the electropositive character of aluminium. An X-ray diffraction analysis revealed a monomeric structure and the shortest Al–K distance hitherto reported. The ultraviolet visible spectrum in combination with density functional theory calculations suggests an electronic structure characterized by a lone pair of electrons and an unoccupied p orbital on the aluminium centre. This species readily deprotonates benzene to form the corresponding (hydrido)(phenyl)aluminate. Reactions with other electrophiles corroborate the nucleophilicity of the aluminium centre. ファイル公開：2020/07/01 |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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