@article{Britovsek:2016:10.1002/chem.201603909,
author = {Britovsek, GJ and McGuinness, DS},
doi = {10.1002/chem.201603909},
journal = {Chemistry - A European Journal},
pages = {16891--16896},
title = {A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways},
url = {http://dx.doi.org/10.1002/chem.201603909},
volume = {22},
year = {2016}
}

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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 by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2 PN(Me)PPh2 and (o-MeC6 H4 )2 PN(Me)P(o-MeC6 H4 )2 . Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1-hexene, 1-octene and the major side products (cyclopentanes and n-alkanes). For the latter ligand, introduction of o-alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o-aryl substituted PNP ligands for trimerization can be rationalized.
AU  - Britovsek,GJ
AU  - McGuinness,DS
DO  - 10.1002/chem.201603909
EP  - 16896
PY  - 2016///
SN  - 0947-6539
SP  - 16891
TI  - A DFT mechanistic study on ethylene tri- and tetramerization with Cr/PNP catalysts: single versus double insertion pathways
T2  - Chemistry - A European Journal
UR  - http://dx.doi.org/10.1002/chem.201603909
UR  - http://www.ncbi.nlm.nih.gov/pubmed/27723144
UR  - http://hdl.handle.net/10044/1/41536
VL  - 22
ER  - 

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