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Homogeneous and Heterogeneous Nickel‐Catalyzed Olefin Oligomerization: Experimental Investigation for a Common Mechanistic Proposition and Catalyst Optimization
Author(s) -
Forget Séverine,
OlivierBourbigou Hélène,
Delcroix Damien
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201700348
Subject(s) - catalysis , homogeneous , nickel , olefin fiber , homogeneous catalysis , ethylene , chemistry , heterogeneous catalysis , combinatorial chemistry , organic chemistry , thermodynamics , physics
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.