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@article{Britovsek:2015:10.1021/acscatal.5b00989,
author = {Britovsek, GJP and McGuinness, DS and Wierenga, TS and Young, CT},
doi = {10.1021/acscatal.5b00989},
journal = {ACS Catalysis},
pages = {4152--4166},
title = {Single- and Double-Coordination Mechanism in Ethylene Tri- and Tetramerization with Cr/PNP Catalysts},
url = {http://dx.doi.org/10.1021/acscatal.5b00989},
volume = {5},
year = {2015}
}

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TY  - JOUR
AB  - The mechanism of ethylene trimerization and tetramerization with a chromium–diphosphinoamine (Cr–PNP) catalyst system has been studied with combined experimental and theoretical methods. Of the total product output, 1-octene, cyclopentanes, n-alkanes, and higher (C10+) olefins are formed with a fractional (∼1.4) order response to ethylene concentration, whereas 1-hexene formation is approximately first-order in ethylene. Theoretical studies suggest a mechanism involving a cationic monometallic catalyst in Cr(I) and Cr(III) formal oxidation states. A key feature of the developed model is the occurrence of a double-coordination mechanism in which a bis(ethylene) chromacyclopentane intermediate is responsible for 1-octene formation as well as the other coproducts that have a greater than first-order response to ethylene. In contrast, 1-hexene is formed primarily from a mono(ethylene) chromacyclopentane intermediate. The selectivity of catalysis is governed by the competition between single- and double-coordination pathways. The mechanistic model developed displays excellent correlation with experimental observations and is able to fully explain the formation of all products generated with this catalyst.
AU  - Britovsek,GJP
AU  - McGuinness,DS
AU  - Wierenga,TS
AU  - Young,CT
DO  - 10.1021/acscatal.5b00989
EP  - 4166
PY  - 2015///
SN  - 2155-5435
SP  - 4152
TI  - Single- and Double-Coordination Mechanism in Ethylene Tri- and Tetramerization with Cr/PNP Catalysts
T2  - ACS Catalysis
UR  - http://dx.doi.org/10.1021/acscatal.5b00989
UR  - http://hdl.handle.net/10044/1/34266
VL  - 5
ER  -

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