DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst

Handle URI:
http://hdl.handle.net/10754/564021
Title:
DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst
Authors:
Pasha, Farhan Ahmad; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Toulhoat, Hervé; De Bruin, Theodorus J M
Abstract:
A computational study within the framework of density functional theory is presented on the oligomerization of ethylene to yield 1-hexene using [(η5-C5H4CMe2C6H5)]TiCl3/MAO] catalyst. This study explicitly takes into account a methylaluminoxane (MAO) cocatalyst model, where the MAO cluster has become an anionic species after having abstracted one chloride anion, yielding a cationic activated catalyst. Hence, the reaction profile was calculated using the zwitterionic system, and the potential energy surface has been compared to the cationic catalytic system. Modest differences were found between the two free energy profiles. However, we show for the first time that the use of a realistic zwitterionic model is required to obtain a Brønsted-Evans-Polanyi relationship between the energy barriers and reaction energies.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
26-Jan-2015
DOI:
10.1021/om5008874
Type:
Article
ISSN:
02767333
Sponsors:
The authors acknowledge OCRF King Abdullah University of Science and Technology (KAUST) KSA for Award No. UK-C0017.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPasha, Farhan Ahmaden
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorToulhoat, Hervéen
dc.contributor.authorDe Bruin, Theodorus J Men
dc.date.accessioned2015-08-03T12:28:46Zen
dc.date.available2015-08-03T12:28:46Zen
dc.date.issued2015-01-26en
dc.identifier.issn02767333en
dc.identifier.doi10.1021/om5008874en
dc.identifier.urihttp://hdl.handle.net/10754/564021en
dc.description.abstractA computational study within the framework of density functional theory is presented on the oligomerization of ethylene to yield 1-hexene using [(η5-C5H4CMe2C6H5)]TiCl3/MAO] catalyst. This study explicitly takes into account a methylaluminoxane (MAO) cocatalyst model, where the MAO cluster has become an anionic species after having abstracted one chloride anion, yielding a cationic activated catalyst. Hence, the reaction profile was calculated using the zwitterionic system, and the potential energy surface has been compared to the cationic catalytic system. Modest differences were found between the two free energy profiles. However, we show for the first time that the use of a realistic zwitterionic model is required to obtain a Brønsted-Evans-Polanyi relationship between the energy barriers and reaction energies.en
dc.description.sponsorshipThe authors acknowledge OCRF King Abdullah University of Science and Technology (KAUST) KSA for Award No. UK-C0017.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleDFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalysten
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionIFP Energies Nouvelles, 1-4 Avenue de Bois PréauRueil-Malmaison, Franceen
kaust.authorBasset, Jean-Marieen
kaust.authorPasha, Farhan Ahmaden
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