Reaction Rate Inside the Cavity of [Ga 4 L 6 ] 12− Supramolecular Metallocage is Regulated by the Encapsulated Solvent
| Autor: | Gregori Ujaque, Gantulga Norjmaa, Jean-Didier Maréchal |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Organic Chemistry Supramolecular chemistry General Chemistry 010402 general chemistry 01 natural sciences Catalysis Reductive elimination 0104 chemical sciences Gibbs free energy Reaction rate Solvent chemistry.chemical_compound Molecular dynamics symbols.namesake chemistry symbols Physical chemistry Phosphine Supramolecular catalysis |
| Zdroj: | Chemistry – A European Journal. 26:6988-6992 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201905608 |
| Popis: | In the present study the dependence of the reaction rate of carbon-carbon reductive elimination from R3 PAu(MeOH)(CH3 )2 (R=Me, Et) complexes inside [Ga4 L6 ]12- metallocage on the nature of the phosphine ligand is investigated by computational means. The reductive elimination mechanism is analyzed in methanol solution and inside the metallocage. Classical molecular dynamics simulations reveal that the smaller the gold complex (which depends on the phosphine ligand size) the larger the number of solvent molecules encapsulated. The size of the phosphine ligands defines the space that is left available inside the cavity that can be occupied by solvent molecules. The Gibbs energy barriers calculated at DFT level, in excellent agreement with experiment both in solution and in the metallocage, show that the presence/absence of explicit solvent molecules inside the cavity significantly modifies the reaction rate. |
| Databáze: | OpenAIRE |
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