Homogeneous and Heterogeneous Nickel‐Catalyzed Olefin Oligomerization: Experimental Investigation for a Common Mechanistic Proposition and Catalyst Optimization. Issue 12 (7th June 2017)

• Record Type: Journal Article
• Authors: Forget, Séverine; Olivier‐Bourbigou, Hélène; Delcroix, Damien
• Is Part Of: ChemCatChem. Volume 9:Issue 12(2017)
• Page Start: 2408
• Page End: 2417
• Publication Date: 2017-06-07
• Subjects: homogeneous and heterogeneous catalysis -- nickel -- NiSiF6 -- oligomerization -- reaction mechanisms; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201700348
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: Only a few catalytic transformations can be efficiently catalyzed by both homogeneous or heterogeneous technologies, with short olefin oligomerization promoted by a nickel‐based catalysts among them. Homogeneous and heterogeneous catalysis are often opposed in terms of activity, active‐site description or recyclability, traditionally mentioned as "homogeneous versus. heterogeneous". Unlike previous studies, we propose to emphasize the similarities between both catalysis by comparing industrially representative results obtained in continuous flow‐mode under similar mild conditions. A detailed analysis of both primary products of olefins oligomerization, and a set of secondary products obtained in experimental assays completed with recently published results of DFT calculations prompted us to postulate a common mechanistic pathway for nickel‐catalyzed ethylene oligomerization. Heterogeneous metallic ethylene oligomerization, for which nickel active sites identification has indeed long been under debate, seems to follow the Cossee–Arlman mechanism, well accepted as major mechanism in the homogeneous counterpart. This analysis allowed us to design an unprecedented heterogeneous catalyst active for ethylene and butene oligomerization. Abstract : Noble nickel : Short olefin oligomerization promoted by a nickel‐based catalysts can be both hetereogeneous and homogeneous. Similarities between both routes are compared to help elucidate the long debated nickel active sites. An unprecedented non‐acidic heterogeneous catalyst active for ethylene and butene oligomerization is designed.