Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity?
The performance of <i>C</i><sub>2</sub>-symmetric <i>ansa</i>-hafnocene catalysts for isotactic polypropylene typically deteriorates at increasing temperature much faster than that of their zirconium analogues. Herein, we analyze in detail a set of five Hf/Zr meta...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-08-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/16/2621 |
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| author | Antonio Vittoria Georgy P. Goryunov Vyatcheslav V. Izmer Dmitry S. Kononovich Oleg V. Samsonov Francesco Zaccaria Gaia Urciuoli Peter H. M. Budzelaar Vincenzo Busico Alexander Z. Voskoboynikov Dmitry V. Uborsky Christian Ehm Roberta Cipullo |
| author_facet | Antonio Vittoria Georgy P. Goryunov Vyatcheslav V. Izmer Dmitry S. Kononovich Oleg V. Samsonov Francesco Zaccaria Gaia Urciuoli Peter H. M. Budzelaar Vincenzo Busico Alexander Z. Voskoboynikov Dmitry V. Uborsky Christian Ehm Roberta Cipullo |
| author_sort | Antonio Vittoria |
| collection | DOAJ |
| description | The performance of <i>C</i><sub>2</sub>-symmetric <i>ansa</i>-hafnocene catalysts for isotactic polypropylene typically deteriorates at increasing temperature much faster than that of their zirconium analogues. Herein, we analyze in detail a set of five Hf/Zr metallocene pairs—including some of the latest generation catalysts—at medium- to high-polymerization temperature. Quantitative structure–activity relationship (QSAR) models for stereoselectivity, the ratio allyl/vinyl chain ends, and 2,1/3,1 misinsertions in the polymer indicate a strong dependence of polymerization performance on electrophilicity of the catalyst, which is a function of the ligand framework and the metal center. Based on this insight, the stronger performance decline of hafnocenes is ascribed to electrophilicity-dependent stabilization effects. |
| first_indexed | 2024-03-10T08:27:28Z |
| format | Article |
| id | doaj.art-8ab03d4ccbdf4edcb07fe55898697f68 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T08:27:28Z |
| publishDate | 2021-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-8ab03d4ccbdf4edcb07fe55898697f682023-11-22T09:21:49ZengMDPI AGPolymers2073-43602021-08-011316262110.3390/polym13162621Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity?Antonio Vittoria0Georgy P. Goryunov1Vyatcheslav V. Izmer2Dmitry S. Kononovich3Oleg V. Samsonov4Francesco Zaccaria5Gaia Urciuoli6Peter H. M. Budzelaar7Vincenzo Busico8Alexander Z. Voskoboynikov9Dmitry V. Uborsky10Christian Ehm11Roberta Cipullo12Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDipartimento di Chimica, Biologia e Biotecnologie and CIRCC, Universitaà di Perugia, 06123 Perugia, ItalyDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, 119991 Moscow, RussiaDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, ItalyThe performance of <i>C</i><sub>2</sub>-symmetric <i>ansa</i>-hafnocene catalysts for isotactic polypropylene typically deteriorates at increasing temperature much faster than that of their zirconium analogues. Herein, we analyze in detail a set of five Hf/Zr metallocene pairs—including some of the latest generation catalysts—at medium- to high-polymerization temperature. Quantitative structure–activity relationship (QSAR) models for stereoselectivity, the ratio allyl/vinyl chain ends, and 2,1/3,1 misinsertions in the polymer indicate a strong dependence of polymerization performance on electrophilicity of the catalyst, which is a function of the ligand framework and the metal center. Based on this insight, the stronger performance decline of hafnocenes is ascribed to electrophilicity-dependent stabilization effects.https://www.mdpi.com/2073-4360/13/16/2621hafnocenesolefin polymerizationiPPmolecular catalystsQSARhigh-temperature performance |
| spellingShingle | Antonio Vittoria Georgy P. Goryunov Vyatcheslav V. Izmer Dmitry S. Kononovich Oleg V. Samsonov Francesco Zaccaria Gaia Urciuoli Peter H. M. Budzelaar Vincenzo Busico Alexander Z. Voskoboynikov Dmitry V. Uborsky Christian Ehm Roberta Cipullo Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? Polymers hafnocenes olefin polymerization iPP molecular catalysts QSAR high-temperature performance |
| title | Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? |
| title_full | Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? |
| title_fullStr | Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? |
| title_full_unstemmed | Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? |
| title_short | Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity? |
| title_sort | hafnium vs zirconium the perpetual battle for supremacy in catalytic olefin polymerization a simple matter of electrophilicity |
| topic | hafnocenes olefin polymerization iPP molecular catalysts QSAR high-temperature performance |
| url | https://www.mdpi.com/2073-4360/13/16/2621 |
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