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

Farhan Ahmad Pasha; Jean-Marie Basset; Hervé Toulhoat; Theodorus J M De Bruin

doi:10.1021/om5008874

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

Farhan Ahmad Pasha, Jean-Marie Basset, Hervé Toulhoat, Theodorus J M De Bruin

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17 Scopus citations

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.

Original language	English (US)
Pages (from-to)	426-431
Number of pages	6
Journal	Organometallics
Volume	34
Issue number	2
DOIs	https://doi.org/10.1021/om5008874
State	Published - Jan 7 2015

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/om5008874

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@article{d102750642404e02b6392180844a8419,

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

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 Br{\o}nsted-Evans-Polanyi relationship between the energy barriers and reaction energies.",

author = "Pasha, {Farhan Ahmad} and Jean-Marie Basset and Herv{\'e} Toulhoat and {De Bruin}, {Theodorus J M}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): UK-C0017 Acknowledgements: The authors acknowledge OCRF King Abdullah University of Science and Technology (KAUST) KSA for Award No. UK-C0017.",

year = "2015",

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doi = "10.1021/om5008874",

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AU - Pasha, Farhan Ahmad

AU - Basset, Jean-Marie

AU - Toulhoat, Hervé

AU - De Bruin, Theodorus J M

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): UK-C0017 Acknowledgements: The authors acknowledge OCRF King Abdullah University of Science and Technology (KAUST) KSA for Award No. UK-C0017.

PY - 2015/1/7

Y1 - 2015/1/7

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/564021

UR - https://pubs.acs.org/doi/10.1021/om5008874

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DO - 10.1021/om5008874

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SN - 0276-7333

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EP - 431

JO - Organometallics

JF - Organometallics

IS - 2

ER -

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

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