2134/23530
Atanas K. Tomov
Atanas K.
Tomov
James D. Nobbs
James D.
Nobbs
Juan J. Chirinos
Juan J.
Chirinos
Prabhjot K. Saini
Prabhjot K.
Saini
Robert Malinowski
Robert
Malinowski
Sarah K.Y. Ho
Sarah K.Y.
Ho
Craig T. Young
Craig T.
Young
David S. McGuinness
David S.
McGuinness
Andrew J.P. White
Andrew J.P.
White
Mark Elsegood
Mark
Elsegood
George J.P. Britovsek
George J.P.
Britovsek
Alternating α-olefin distributions via single and double insertions in chromium-catalyzed ethylene oligomerization
Loughborough University
2016
untagged
Chemical Sciences not elsewhere classified
Inorganic Chemistry
Organic Chemistry
2016-12-20 12:37:56
Journal contribution
https://repository.lboro.ac.uk/articles/journal_contribution/Alternating_-olefin_distributions_via_single_and_double_insertions_in_chromium-catalyzed_ethylene_oligomerization/9390530
The catalytic oligomerization of ethylene with chromium-based complexes containing bis(benzimidazolemethyl)amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol–1 h–1 bar–1) with N-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe3 and the N-methyl BIMA ligand 2 have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions.