Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis

A combination of high-throughput experimentation (HTE), surface organometallic chemistry (SOMC) and statistical data analysis provided the platform to analyzein situsilica-grafted Mo imido alkylidene catalysts based on a library of 35 phenols. Overall, these tools allowed for the identification of sigma-donor electronic effects and dispersive interactions and as key drivers in a prototypical metathesis reaction, homodimerization of 1-nonene. Univariate and multivariate correlation analysis confirmed the categorization of the catalytic data into two groups, depending on the presence of aryl groups inorthoposition of the phenol ligand. The initial activity (TOFin) was predominantly correlated to the sigma-donor ability of the aryloxy ligands, while the overall catalytic performance (TON1 h) was mainly dependent on attractive dispersive interactions with the used phenol ligands featuring arylorthosubstituents and, in sharp contrast, repulsive dispersive interactions with phenol free of arylorthosubstituents. This work outlines a fast and efficient workflow of gaining molecular-level insight into supported metathesis catalysts and highlights sigma-donor ability and noncovalent interactions as crucial properties for designing active d(0)supported metathesis catalysts.