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

Autor(es)

Silva, Jordan De Jesus ^[1] ; Ferreira, Marco A. B. ^{[2, 3]} ; Fedorov, Alexey ^{[1, 4]} ; Sigman, Matthew S. ^[2] ; Coperet, Christophe ^[1]

Afiliação do(s) autor(es)

^[1] Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Vladimir Prelog Weg 1 5, CH-8093 Zurich - Switzerland

^[2] Univ Utah, Dept Chem, 315 South 1400 East, Salt Lake City, UT 84112 - USA

^[3] Fed Univ Sao Carlos UFSCar, Ctr Excellence Res Sustainable Chem CERSusChem, Dept Chem, Rodovia Washington Luis, Km 235, SP-310, BR-13565905 Sao Carlos, SP - Brazil

^[4] Swiss Fed Inst Technol, Dept Mech & Proc Engn, Leanhardstr 21, CH-8092 Zurich - Switzerland

• Tipo de documento: Artigo Científico
• Fonte: CHEMICAL SCIENCE; v. 11, n. 26, p. 6717-6723, JUL 14 2020.
• Citações Web of Science: 0

Resumo

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. (AU)

• Processo FAPESP: 17/13306-1 - Síntese assimétrica de heterociclos via reações de nucleopaladação: Desenvolvimento, designe racional de ligantes quirais e estudos mecanísticos
• Beneficiário: Marco Antonio Barbosa Ferreira
• Modalidade de apoio: Bolsas no Exterior - Pesquisa
• Processo FAPESP: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock
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• Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia
• Processo FAPESP: 15/08541-6 - Ressonância magnética nuclear: além da determinação estrutural
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