DFT insight into metals and ligands substitution effects on reactivity of phenoxy-imine catalysts for ethylene polymerization

Apilardmongkol, Pavee; Ratanasak, Manussada; Hasegawa, Jun-ya; Parasuk, Vudhichai

DFT insight into metals and ligands substitution effects on reactivity of phenoxy-imine catalysts for ethylene polymerization

Apilardmongkol, Pavee; Ratanasak, Manussada; Hasegawa, Jun-ya et al.

Journal of Molecular Graphics and Modelling, 2023, 125

Permalink : https://hdl.handle.net/2115/97058

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アクセス権	open access
URI	https://hdl.handle.net/2115/97058
タイトル	DFT insight into metals and ligands substitution effects on reactivity of phenoxy-imine catalysts for ethylene polymerization
著者	Apilardmongkol, Pavee ; Ratanasak, Manussada ; Hasegawa, Jun-ya ; Parasuk, Vudhichai
著者名 Apilardmongkol, Pavee
著者名 Ratanasak, Manussada
e-Rad_Researcher 30322168 著者名 Hasegawa, Jun-ya
著者名 Parasuk, Vudhichai
言語	英語
キーワード	FI catalyst
	Ethylene polymerization
	DFT calculations
	Nickel
	Mechanism
発行日	2023-12
出版者	Elsevier
収録物名	Journal of Molecular Graphics and Modelling
巻(号)	125
抄録	The reaction mechanism of ethylene (ET) polymerization catalyzed by the phenoxy-imine (FI) ligands using DFT calculations was studied. Among five possible isomers, isomer A which has an octahedral geometry and a (cis-N/trans-O/cis-Cl) arrangement is the most stable pre-reaction Ti-FI dichloride complex. The isomer A can be activated by MAO to form the active catalyst and the active form was used for the study of the mechanism for Ti-FI. The second ethylene insertion was found to be the rate-determining step of the catalyzed ethylene polymerization. To examine the effect of group IVB transition metals (M = Ti, Zr, Hf) substitutions, calculated activation energies at the rate-determining step (E-a(RDS)) were compared, where values of E-a(RDS) of Zr < Hf < Ti agree with experiments. Moreover, we examined the effect of substitution on (O, X) ligands of the Ti-phenoxy-imine (Ti-1) based catalyst. The results revealed that E-a(RDS) of (O, N) > (O, O) > (O, P) > O, S). Hence, the (O, S) ligand has the highest potential to improve the catalytic activity of the Ti-FI catalyst. We also found the activation energy to be related to the Ti-X distance. In addition, a novel Ni-based FI catalyst was investigated. The results indicated that the nickel (II) complex based on the phenoxy-imine (O, N) ligand in the square-planar geometry is more active than in the octahedral geometry. This work provides fundamental insights into the reaction mechanism of M - FI catalysts which can be used for the design and development of M - FI catalysts for ET polymerization.
資源タイプ	学術雑誌論文
出版タイプ	Accepted Manuscript
権利情報	Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
権利情報	©2023, Elsevier. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
PISSN	1093-3263
関連情報 (isVersionOf)	出版社版DOI https://doi.org/10.1016/j.jmgm.2023.108586