Four Cl/Me substituted [ONNO] Zr-catalysts have been tested in ethene/α-olefin polymerization. Replacing electron-donating methyl with isosteric but electron-withdrawing chlorine substituents results in a significant increase of comonomer incorporation. Exploration of steric and electronic properties of the ancillary ligand by DFT confirm that relative reactivity ratios are mainly determined by the electrophilicity of the metal center. Furthermore, quantitative DFT modeling of propagation barriers that determine polymerization kinetics reveals that electronic effects observed in these catalysts affect relative barriers for insertion and a capture-like transition state (TS).

Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts / Zaccaria, Francesco; Cipullo, Roberta; Correa, Andrea; Budzelaar, P. H. M.; Busico, Vincenzo; Ehm, Christian. - In: PROCESSES. - ISSN 2227-9717. - 7:6(2019), pp. 384-397. [10.3390/pr7060384]

Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts

Zaccaria, Francesco;Cipullo, Roberta;Correa, Andrea;Budzelaar, P. H. M.;Busico, Vincenzo;Ehm, Christian
2019

Abstract

Four Cl/Me substituted [ONNO] Zr-catalysts have been tested in ethene/α-olefin polymerization. Replacing electron-donating methyl with isosteric but electron-withdrawing chlorine substituents results in a significant increase of comonomer incorporation. Exploration of steric and electronic properties of the ancillary ligand by DFT confirm that relative reactivity ratios are mainly determined by the electrophilicity of the metal center. Furthermore, quantitative DFT modeling of propagation barriers that determine polymerization kinetics reveals that electronic effects observed in these catalysts affect relative barriers for insertion and a capture-like transition state (TS).
2019
Separating Electronic from Steric Effects in Ethene/α-Olefin Copolymerization: A Case Study on Octahedral [ONNO] Zr-Catalysts / Zaccaria, Francesco; Cipullo, Roberta; Correa, Andrea; Budzelaar, P. H. M.; Busico, Vincenzo; Ehm, Christian. - In: PROCESSES. - ISSN 2227-9717. - 7:6(2019), pp. 384-397. [10.3390/pr7060384]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11588/757112
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