Homogeneous and Heterogeneous Nickel-Catalyzed Olefin Oligomerization: Experimental Investigation for a Common Mechanistic Proposition and Catalyst Optimization

International audienceOnly a few catalytic transformations can be efficiently catalyzedby both homogeneous or heterogeneous technologies,with short olefin oligomerization promoted by a nickel-basedcatalysts among them. Homogeneous and heterogeneous catalysisare often opposed in terms of activity, active-site descriptionor recyclability, traditionally mentioned as “homogeneousversus. heterogeneous”. Unlike previous studies, we proposeto emphasize the similarities between both catalysis by comparingindustrially representative results obtained in continuousflow-mode under similar mild conditions. A detailed analysisof both primary products of olefins oligomerization, anda set of secondary products obtained in experimental assayscompleted with recently published results of DFT calculationsprompted us to postulate a common mechanistic pathway fornickel-catalyzed ethylene oligomerization. Heterogeneous metallicethylene oligomerization, for which nickel active sitesidentification has indeed long been under debate, seems tofollow the Cossee–Arlman mechanism, well accepted as majormechanism in the homogeneous counterpart. This analysis allowedus to design an unprecedented heterogeneous catalystactive for ethylene and butene oligomerization