Relationship between the Structure of Fluorine-Containing Phenoxy-Imine Complexes, Their Spectral Properties and Activity in Ethylene Polymerization Full article
| Journal |
Polymer Science Series B
ISSN: 1560-0904 , E-ISSN: 1531-8583 |
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| Output data | Year: 2022, Volume: 64, Number: 6, Pages: 779–790 Pages count : 12 DOI: 10.1134/S1560090422700555 | ||
| Tags | Catalyst activity; Fourier transform infrared spectroscopy; Ligands; Molecular orbitals; Organometallics; Polymerization; Synthesis (chemical); Titanium compounds | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0008 |
Abstract:
This paper describes a series of novel post-metallocene titanium complexes catalyzing ethylene polymerization. Five titanium complexes bearing fluorine-containing phenoxy-imines were synthesized from Ti(i-PrO)2Cl2 and corresponding ligands in good yields (50–70%). Systematic investigations of structure–activity relationships were performed via quantum-chemical calculations, FTIR spectroscopy and experimental tests. FTIR spectroscopy revealed that the complexes with polyfluorobenzene moieties contain η2(N, O)-coordinated ligands, while only one of the two imine nitrogens is bound to a Ti atom in complex with heptafluronaphtyl moieties. The ONIOM (BP86/6-31G:PM6) computational approach was used to optimize the structure of titanium complexes and to calculate their infrared spectra and frontier molecular orbitals. We found that energy gaps between frontier orbitals (HOMO and LUMO) in the polyfluorinated dichloride titanium complexes correlated with the experimental activity values. The correlation provides a qualitative estimate of the catalytic activity for design of new polyfluorinated titanium complexes.
Cite:
Fursov E.A.
, Shabalin A.Y.
, Potapov A.G.
, Chesalov Y.A.
, Prikhod'ko S.A.
, Adonin N.Y.
Relationship between the Structure of Fluorine-Containing Phenoxy-Imine Complexes, Their Spectral Properties and Activity in Ethylene Polymerization
Polymer Science Series B. 2022. V.64. N6. P.779–790. DOI: 10.1134/S1560090422700555 WOS Scopus РИНЦ AN OpenAlex
Relationship between the Structure of Fluorine-Containing Phenoxy-Imine Complexes, Their Spectral Properties and Activity in Ethylene Polymerization
Polymer Science Series B. 2022. V.64. N6. P.779–790. DOI: 10.1134/S1560090422700555 WOS Scopus РИНЦ AN OpenAlex
Dates:
| Submitted: | Sep 5, 2022 |
| Accepted: | Oct 22, 2022 |
| Published print: | Dec 1, 2022 |
| Published online: | Dec 12, 2022 |
Identifiers:
| Web of science: | WOS:000898278900001 |
| Scopus: | 2-s2.0-85143769032 |
| Elibrary: | 50321339 |
| Chemical Abstracts: | 2022:3106343 |
| OpenAlex: | W4311156759 |