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.