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@article{Tomov:2016:10.1021/acs.organomet.6b00671,
author = {Tomov, AK and Nobbs, JD and Chirinos, JJ and Saini, PK and Malinowski, R and Ho, SKY and Young, CT and McGuinness, DS and White, AJP and Elsegood, MRJ and Britovsek, GJP},
doi = {10.1021/acs.organomet.6b00671},
journal = {Organometallics},
pages = {510--522},
title = {Alternating alpha-olefin distributions via single and double insertions in chromium-catalyzed ethylene oligomerization.},
url = {http://dx.doi.org/10.1021/acs.organomet.6b00671},
volume = {36},
year = {2016}
}

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TY  - JOUR
AB  - 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 (>100000 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.
AU  - Tomov,AK
AU  - Nobbs,JD
AU  - Chirinos,JJ
AU  - Saini,PK
AU  - Malinowski,R
AU  - Ho,SKY
AU  - Young,CT
AU  - McGuinness,DS
AU  - White,AJP
AU  - Elsegood,MRJ
AU  - Britovsek,GJP
DO  - 10.1021/acs.organomet.6b00671
EP  - 522
PY  - 2016///
SN  - 0276-7333
SP  - 510
TI  - Alternating alpha-olefin distributions via single and double insertions in chromium-catalyzed ethylene oligomerization.
T2  - Organometallics
UR  - http://dx.doi.org/10.1021/acs.organomet.6b00671
UR  - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000394198100004&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - http://hdl.handle.net/10044/1/60063
VL  - 36
ER  -

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