A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

Naeimeh Bahri-Laleh; Mehdi Nekoomanesh-Haghighi; Seyed Amin Mirmohammadi

doi:10.1016/j.jorganchem.2012.08.017

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

Naeimeh Bahri-Laleh, Mehdi Nekoomanesh-Haghighi, Seyed Amin Mirmohammadi

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Abstract

Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

Original language	English (US)
Pages (from-to)	74-79
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	719
DOIs	https://doi.org/10.1016/j.jorganchem.2012.08.017
State	Published - Nov 2012
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The authors thank MOLNAK (www.molnac.unisa.it) for its computer facilities. NBL thanks professor Luigi Cavallo (University of Salerno and King Abdullah University of Science and Technology) for his scientific support.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1016/j.jorganchem.2012.08.017

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title = "A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst",

abstract = "Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. {\textcopyright} 2012 Elsevier B.V.",

author = "Naeimeh Bahri-Laleh and Mehdi Nekoomanesh-Haghighi and Mirmohammadi, {Seyed Amin}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The authors thank MOLNAK (www.molnac.unisa.it) for its computer facilities. NBL thanks professor Luigi Cavallo (University of Salerno and King Abdullah University of Science and Technology) for his scientific support. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2012",

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doi = "10.1016/j.jorganchem.2012.08.017",

language = "English (US)",

volume = "719",

pages = "74--79",

journal = "Journal of Organometallic Chemistry",

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T1 - A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

AU - Bahri-Laleh, Naeimeh

AU - Nekoomanesh-Haghighi, Mehdi

AU - Mirmohammadi, Seyed Amin

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The authors thank MOLNAK (www.molnac.unisa.it) for its computer facilities. NBL thanks professor Luigi Cavallo (University of Salerno and King Abdullah University of Science and Technology) for his scientific support. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2012/11

Y1 - 2012/11

N2 - Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

AB - Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

Abstract

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