Non-Covalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis.

08:00 EDT 10th June 2019 | BioPortfolio

Summary of "Non-Covalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis."

High-throughput experimentation and multivariate modelling allow identification of non-covalent interactions (NCIs) in monoaryloxy-pyrrolide Mo imido alkylidene metathesis catalysts prepared in situ as a key driver for high activity in a representative crossmetathesis reaction (homodimerization of 1-nonene). Statistical univariate and multivariate modelling categorizes catalytic data from 35 phenolic ligands into two groups, depending on the substitution in the ortho position of the phenol ligand. Catalytic activity descriptor TON1h correlates predominantly with attractive NCIs when ortho aryl phenols are used 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.


Journal Details

This article was published in the following journal.

Name: Journal of the American Chemical Society
ISSN: 1520-5126


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