Towards Naked Zinc(II) in the Condensed Phase: A Highly Lewis Acidic Zn II Dication Stabilized by Weakly Coordinating Carborate Anions
| Autor: | Béatrice Jacques, Rudolf J. Wehmschulte, Thibault Damiens, Nicolas Adet, David Specklin, Christophe Gourlaouen, Samuel Dagorne |
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| Přispěvatelé: | Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Hydrosilylation 010405 organic chemistry Chemistry chemistry.chemical_element General Chemistry Nuclear magnetic resonance spectroscopy Zinc General Medicine [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry 01 natural sciences Catalysis Phase synthesis 0104 chemical sciences Dication chemistry.chemical_compound Polymer chemistry Reactivity (chemistry) Lewis acids and bases Counterion Fluoride ComputingMilieux_MISCELLANEOUS Zinc cation |
| Zdroj: | Angewandte Chemie International Edition Angewandte Chemie International Edition, Wiley-VCH Verlag, In press, ⟨10.1002/anie.202012287⟩ |
| ISSN: | 1521-3757 0044-8249 1433-7851 1521-3773 |
| DOI: | 10.1002/ange.202012287 |
| Popis: | The employment of the hexyl-substituted anion [HexCB11 Cl11 ]- allowed the synthesis of a ZnII species, Zn[HexCB11 Cl11 ]2 , 3, in which the Zn2+ cation is only weakly coordinated to two carborate counterions and that is soluble in low polarity organic solvents such as bromobenzene. DOSY NMR studies show the facile displacement of at least one of the counterions, and this near nakedness of the cation results in high catalytic activity in the hydrosilylation of 1-hexene and 1-methyl-1cyclohexene. Fluoride ion affinity (FIA) calculations reveal a solution Lewis acidity of 3 (FIA=262.1 kJ mol-1 ) that is higher than that of the landmark Lewis acid B(C6 F5 )3 (FIA=220.5 kJ mol-1 ). This high Lewis acidity leads to a high activity in catalytic CO2 and Ph2 CO reduction by Et3 SiH and hydrogenation of 1,1-diphenylethylene using 1,4-cyclohexadiene as the hydrogen source. Compound 3 was characterized by multinuclear NMR spectroscopy, mass spectrometry, single crystal X-ray diffraction, and DFT studies. |
| Databáze: | OpenAIRE |
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