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Fluxional bis(phenoxy-imine) Zr and Ti catalysts for polymerization

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Abstract

Bis(phenoxy-imine) complexes of zirconium or titanium, a type of Fenokishi-Imin catalysts, allow the production of polyethylenes with well-defined bimodal molecular weight distributions. Interestingly, by substitution of phenyl rings in the bis(phenoxy-imine) ligands by perfluorinated phenyl rings, the polymerization reaches a desired unimodal behavior. These catalysts have three isomers of similar energy that can be easily interconverted. It is likely that the bimodal behavior is due to the coexistence of more than one isomer in the reaction vessel. Here, we perform static and dynamic DFT calculations to understand the isomerization of the catalytic active species. We analyze the relative Gibbs energies of the different isomers and the barriers for the isomerization processes. Further characterization of the isomers is obtained through stereo maps, aromaticity measures, and NCI plots. Our results show that by changing the phenyl group by a perfluorinated phenyl ring, one of the isomers is particularly stabilized, thus explaining the unimodal behavior of the polyethylene production process.

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Acknowledgements

S.E. acknowledges financial support through IFUG2019 Ph.D. fellowship from Universitat de Girona (UdG) and Donostia International Physics Center (DIPC). A.P. is a Serra Húnter Fellow. A.P. and M.S. thank the Ministerio de Economía y Competitividad (MINECO) of Spain for projects CTQ2014-59832-JIN, PGC2018-097722-B-I00 and CTQ2017-85341-P; Generalitat de Catalunya for project 2017SGR39, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia prize 2019 to A.P. N.B.-L. appreciates Iran Polymer and Petrochemical Institute (IPPI) for all of the supports provided under the Grant Number of 43794110. We thank support by Mitsui Chemicals, Inc.

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Authors and Affiliations

  1. Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/Maria Aurèlia Capmany 69, 17003, Girona, Catalonia, Spain

    Sílvia Escayola, Artur Brotons-Rufes, Francesco Ragone, Miquel Solà & Albert Poater

  2. Donostia International Physics Center (DIPC), Donostia, Euskadi, Spain

    Sílvia Escayola

  3. Polymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran

    Naeimeh Bahri-Laleh

  4. Department of Chemistry and Biology, University of Salerno, Via Ponte don Melillo, 84084, Fisciano, Italy

    Francesco Ragone & Luigi Cavallo

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  1. Sílvia Escayola
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  5. Luigi Cavallo
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Correspondence to Luigi Cavallo, Miquel Solà or Albert Poater.

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Escayola, S., Brotons-Rufes, A., Bahri-Laleh, N. et al. Fluxional bis(phenoxy-imine) Zr and Ti catalysts for polymerization. Theor Chem Acc 140, 49 (2021). https://doi.org/10.1007/s00214-021-02747-8

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