Noncovalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis
| Autor: | Alexey Fedorov, Jordan De Jesus Silva, Christophe Copéret, Samantha Grosslight, Matthew S. Sigman, Marco A. B. Ferreira |
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| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Chemistry Ligand Aryl General Chemistry 010402 general chemistry Metathesis 01 natural sciences Biochemistry Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Electronic effect Salt metathesis reaction Phenol Non-covalent interactions |
| Zdroj: | Journal of the American Chemical Society, 141 (27) |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | High-throughput experimentation and multivariate modeling allow identification of noncovalent interactions (NCIs) in monoaryloxy-pyrrolide Mo imido alkylidene metathesis catalysts prepared in situ as a key driver for high activity in a representative metathesis reaction (homodimerization of 1-nonene). Statistical univariate and multivariate modeling categorizes catalytic data from 35 phenolic ligands into two groups, depending on the substitution in the ortho position of the phenol ligand. The catalytic activity descriptor TON1h correlates predominantly with attractive NCIs when phenols bear ortho aryl substituents and, conversely, with repulsive NCIs when the phenol has no aryl ortho substituents. Energetic span analysis is deployed to relate the observed NCI and the cycloreversion metathesis step such that aryloxide ligands with no ortho aryls mainly impact the energy of metallacyclobutane intermediates (SP/TBP isomers), whereas aryloxides with pendant ortho aryls influence the transition state energy for the cycloreversion step. While the electronic effects from the aryloxide ligands also play a role, our work outlines how NCIs may be exploited for the design of improved d0 metathesis catalysts. |
| Databáze: | OpenAIRE |
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