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Understanding Alkene Interaction with Metal-Modified Zeolites: Thermodynamics and Mechanism of Bonding in the π-Complex Научная публикация

Журнал Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X
Вых. Данные Год: 2024, Том: 63, Номер: 11, Страницы: 5083–5097 Страниц : 15 DOI: 10.1021/acs.inorgchem.3c04611
Ключевые слова Charge transfer; Chemical bonds; Molecules; Positive ions; Quantum chemistry; Thermodynamics; Zeolites
Авторы Gabrienko Anton A. 1 , Kvasova Ekaterina S. 1,2 , Kolokolov Daniil I. 1,2 , Gorbunov Dmitry E. 3 , Nizovtsev Anton S. 4,2 , Lashchinskaya Zoya N. 1 , Stepanov Alexander G. 1
Организации
1 Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2 Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3 Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Institutskaya Street 3, Novosibirsk 630090, Russia
4 Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 3, Novosibirsk 630090, Russia

Информация о финансировании (1)

1 Российский научный фонд 21-73-10013

Реферат: Zeolites modified with metal cations are perspective catalysts for converting light alkenes to valuable chemicals. A crucial step of the transformation is an alkene interaction with zeolite to afford π-complex with metal cations. The mechanism of alkene bonding with cations is still unclear. To address this problem, propene adsorption on H+ (Bro̷nsted acid site), Na+, Ca2+, Zn2+, Co2+, Cu2+, Cu+, and Ag+ cationic sites in ZSM-5 zeolite has been studied by quantum chemical calculations in terms of adsorption enthalpy, νC═C frequency, and natural bond orbital (NBO) analysis together with natural energy decomposition analysis (NEDA). It is revealed that the conventional concept of σ- and π-bonding is only partially applicable to alkene interaction with metal cations in zeolites. The orbital interaction between an alkene molecule and a metal site is more complex. Several different bonding mechanisms have been identified depending on the nature and electron configuration of the metal cation. This finding explains the complex correlations observed for propene π-complex stability and νC═C frequency shift or charge transfer from the alkene molecule. The results provide the basis for further understanding the interactions between alkenes and inorganic solid Bro̷nsted and Lewis acids.
Библиографическая ссылка: Gabrienko A.A. , Kvasova E.S. , Kolokolov D.I. , Gorbunov D.E. , Nizovtsev A.S. , Lashchinskaya Z.N. , Stepanov A.G.
Understanding Alkene Interaction with Metal-Modified Zeolites: Thermodynamics and Mechanism of Bonding in the π-Complex
Inorganic Chemistry. 2024. V.63. N11. P.5083–5097. DOI: 10.1021/acs.inorgchem.3c04611 WOS Scopus РИНЦ CAPlusCA PMID OpenAlex
Даты:
Поступила в редакцию: 28 дек. 2023 г.
Принята к публикации: 26 февр. 2024 г.
Опубликована online: 7 мар. 2024 г.
Опубликована в печати: 18 мар. 2024 г.
Идентификаторы БД:
Web of science: WOS:001181878300001
Scopus: 2-s2.0-85187338343
РИНЦ: 66473755
Chemical Abstracts: 2024:519380
Chemical Abstracts (print): 186:297823
PMID (PubMed): 38453174
OpenAlex: W4392590617
Цитирование в БД:
БД Цитирований
Scopus 2
Web of science 2
Альметрики: