Noncovalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis

Author(s)

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

Affiliation

^[1] Fed Univ Sao Carlos UFSCar, Dept Chem, Rodovia Washington Luis, Km 235, BR-13565905 Sao Carlos, SP - Brazil

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

^[3] Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Vladimir Prelog Weg 1-5, CH-8093 Zurich - Switzerland

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

• Document type: Journal article
• Source: Journal of the American Chemical Society; v. 141, n. 27, p. 10788-10800, JUL 10 2019.
• Web of Science Citations: 1

Abstract

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 d(0) metathesis catalysts. (AU)

• FAPESP's process: 17/13306-1 - Asymmetric synthesis of heterocycles via nucleopaladation reactions: Development, rational design of chiral ligands and mechanistic studies
• Grantee: Marco Antonio Barbosa Ferreira
• Support Opportunities: Scholarships abroad - Research
• FAPESP's process: 15/08541-6 - Nuclear magnetic resonance spectroscopy: beyond molecular structure assignment
• Grantee: Claudio Francisco Tormena
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock
• Grantee: Arlene Gonçalves Corrêa
• Support Opportunities: Research Grants - Research Centers in Engineering Program