Facile Benzene Reduction by a Ca2+ /AlI Lewis Acid/Base Combination
| Autor: | Wolfgang Donaubauer, Sjoerd Harder, Holger Elsen, Steffen Brand, Frank Hampel, Jens Langer |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
Double bond 010405 organic chemistry General Medicine General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Frustrated Lewis pair 0104 chemical sciences Solvent Metal chemistry.chemical_compound chemistry Nucleophile visual_art visual_art.visual_art_medium Chelation Lewis acids and bases Benzene |
| Zdroj: | Angewandte Chemie International Edition. 57:14169-14173 |
| ISSN: | 1433-7851 |
| Popis: | Attempted synthesis of the donor-acceptor complex (BDI)Ca+ ←AlI (BDI) complex by reaction of (BDI)Ca+ in the form of its B(C6 F5 )4- salt with (BDI)AlI in benzene led to dearomatization of the solvent and formation of (BDI)Ca+ (C6 H6 )AlIII (BDI) (BDI=CH[C(CH3 )N-Dipp]2 , Dipp=2,6-diisopropylphenyl). The C6 H62- anion is strongly puckered and its boat form features four long (ca. 1.50 A) and two short (ca. 1.34 A) C-C bond distances. The flagpole positions of the C6 H62- anion chelate an AlIII cation giving a norbornadiene-like fragment with Al in the 7-position. The C=C double bonds of this alumina-norbornadiene strongly coordinate to the Ca2+ metal ion. The complex is stable in solution up to 80 °C. Several mechanisms for its formation are discussed including a highly likely frustrated Lewis pair type mechanism in which benzene is activated by the Lewis acid (BDI)Ca+ followed by nucleophilic attack by the Lewis base (BDI)AlI . |
| Databáze: | OpenAIRE |
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