Understanding Alkene Interaction with Metal-Modified Zeolites: Thermodynamics and Mechanism of Bonding in the π-Complex | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2024, Volume: 63, Number: 11, Pages: 5083–5097 Pages count : 15 DOI: 10.1021/acs.inorgchem.3c04611

Tags

Charge transfer; Chemical bonds; Molecules; Positive ions; Quantum chemistry; Thermodynamics; Zeolites

Authors

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

Affiliations

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

Funding (1)

Russian Science Foundation

21-73-10013

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.

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 ANCAN PMID OpenAlex

Submitted:	Dec 28, 2023
Accepted:	Feb 26, 2024
Published online:	Mar 7, 2024
Published print:	Mar 18, 2024

Web of science:	WOS:001181878300001
Scopus:	2-s2.0-85187338343
Elibrary:	66473755
Chemical Abstracts:	2024:519380
Chemical Abstracts (print):	186:297823
PMID:	38453174
OpenAlex:	W4392590617

DB	Citing
Scopus	2
Web of science	2