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The role of ion-pair on the olefin polymerization reactivity of zirconium bis(phenoxy-imine) catalyst: quantum mechanical study and its beyond

  • Soumen Saha , Kentaro Matsumoto , Masayoshi Takayanagi , Hirokazu Moriya , Nana Misawa , Nobuaki Koga EMAIL logo and Masataka Nagaoka ORCID logo EMAIL logo
Published/Copyright: June 25, 2025
Pure and Applied Chemistry
From the journal Pure and Applied Chemistry Volume 97 Issue 9

Abstract

Owing to the progress of quantum mechanical (QM) calculations, we have investigated, for the first time, the geometric structure of an ion-pair consisting of the Zr phenoxy-imine (Zr–FI) cation and the borate anion. Further, a number of different structures for ‘Cation & Monomer’, ‘Ion-Pair’, and ‘Ion-Pair & Monomer’ systems have also been studied. The obtained preferred structures of these systems indicate the formation of an octahedral geometry around the Zr-atom. In addition, the counter anion (CA) is preferably located on trans to the Me group of the cation. This allows more space for ethylene insertion to the active Zr-C center, leading to high ethylene polymerization activity. Furthermore, from the calculated interaction energy, we have found weaker interaction between the Zr–FI cation and the CA than in the zirconocene catalysts, making the ion separation easier and facilitating the monomer coordination to the metal. We also investigated the electronic characteristics of the cation–anion interactions and have shown that (i) the molecular orbital interaction, (ii) the charge transfer between the cation and the anion, and (iii) the non-covalent bond interaction are also crucial factors in determining the ion-pair structure. In conclusion, the usefulness and necessity of QM investigation of the ion-pair structures have become evident. Therefore, we assert that while studying the reactivity of catalysts based on their geometric structures, today, one must model at least the ion-pair structure in the QM calculations. Finally, we touch on the brand-new study using the Red Moon simulation, which would become a new possible computational molecular technology (CMT), with the help of thorough research using the QM calculations, an established CMT.

Keywords: Borate anion; FI catalyst; ion-pair; non-covalent interaction; polymerization; quantum mechanical calculation; Quantum Science and Technology
Corresponding authors: Nobuaki Koga, Graduate School of Informatics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan; and Core Research for Evolutional Science and Technology, Japan Science and Technology Agency, Honmachi, Kawaguchi 332-0012, Japan, e-mail: ; and Masataka Nagaoka, Graduate School of Informatics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan; Core Research for Evolutional Science and Technology, Japan Science and Technology Agency, Honmachi, Kawaguchi 332-0012, Japan; and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University Katsura, Kyoto 615-8520, Japan, e-mail:
Article note: A collection of invited papers to celebrate the UN’s proclamation of 2025 as the International Year of Quantum Science and Technology.

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The authors state no conflict of interest.

  6. Research funding: This work was supported by the Core Research for Evolutional Science and Technology (CREST) “Establishment of Computational Molecular Technology towards Macroscopic Chemical Phenomena” of the Japan Science Technology Agency (JST) and partially by the JST ACT-X program “Trans-Scale Approach Toward Materials Innovation” (Grant Number: JPMJAX24DM). It was also supported by a Grant-in-Aid for Science Research from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) in Japan; and also by the MEXT programs “Elements Strategy Initiative for Catalysts and Batteries (ESICB)” (Grant Number JPMXP0112101003), and “Program for Promoting Researches on the Supercomputer Fugaku” (Fugaku battery & Fuel Cell Project) (Grant Number JPMXP1020200301), and additionally by Fugaku Small-Scale Projects (General Research Projects: “Computational Chemical Study for Designing Polymer Materials toward Bond Formation and Cleavage Control” (hp200325) and “Investigation of Parallel Computational Efficiency in Molecular Dynamics Simulations of Adult Human Hemoglobin” (hp210330)) from the Research Organization for Information Science and Technology (RIST). The calculations were partially performed using the computing systems at the Information Technology Center at Nagoya University and also at the Research Center for Computational Science at the Institute for Molecular Science, Okazaki, Japan.

  7. Data availability: Not applicable.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/pac-2025-0463).

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Received: 2025-03-20
Accepted: 2025-06-03
Published Online: 2025-06-25
Published in Print: 2025-09-25

© 2025 IUPAC & De Gruyter

Articles in the same Issue

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  2. IUPAC Technical Report
  3. Acid dissociation constants in selected dipolar non-hydrogen-bond-donor solvents (IUPAC Technical Report)
  4. Preface
  5. Introduction to the Special Issue of “The International Year of Quantum”
  6. Review Articles
  7. Quantum chemistry of molecules in solution. A brief historical perspective
  8. From Hückel to Clar: a block-localized description of aromatic systems
  9. Exploring potential energy surfaces
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  13. When theory came first: a review of theoretical chemical predictions ahead of experiments
  14. Research Articles
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  16. Molecular aromaticity: a quantum phenomenon
  17. Using topology for understanding your computational results
  18. The role of ion-pair on the olefin polymerization reactivity of zirconium bis(phenoxy-imine) catalyst: quantum mechanical study and its beyond
  19. Theoretical insights on the structure and stability of the [C2, H3, P, O] isomeric family
https://doi.org/10.1515/pac-2025-0463
Keywords for this article
Borate anion; FI catalyst; ion-pair; non-covalent interaction; polymerization; quantum mechanical calculation; Quantum Science and Technology

Articles in the same Issue

  1. Frontmatter
  2. IUPAC Technical Report
  3. Acid dissociation constants in selected dipolar non-hydrogen-bond-donor solvents (IUPAC Technical Report)
  4. Preface
  5. Introduction to the Special Issue of “The International Year of Quantum”
  6. Review Articles
  7. Quantum chemistry of molecules in solution. A brief historical perspective
  8. From Hückel to Clar: a block-localized description of aromatic systems
  9. Exploring potential energy surfaces
  10. Unlocking the chemistry facilitated by enzymes that process nucleic acids using quantum mechanical and combined quantum mechanics–molecular mechanics techniques
  11. Hypothetical heterocyclic carbenes
  12. Is relativistic quantum chemistry a good theory of everything?
  13. When theory came first: a review of theoretical chemical predictions ahead of experiments
  14. Research Articles
  15. Exploring reaction dynamics involving post-transition state bifurcations based on quantum mechanical ambimodal transition states
  16. Molecular aromaticity: a quantum phenomenon
  17. Using topology for understanding your computational results
  18. The role of ion-pair on the olefin polymerization reactivity of zirconium bis(phenoxy-imine) catalyst: quantum mechanical study and its beyond
  19. Theoretical insights on the structure and stability of the [C2, H3, P, O] isomeric family
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