TY - JOUR

T1 - Understanding Alkene Interaction with Metal-Modified Zeolites: Thermodynamics and Mechanism of Bonding in the π-Complex

AU - Gabrienko, Anton A.

AU - Kvasova, Ekaterina S.

AU - Kolokolov, Daniil I.

AU - Gorbunov, Dmitry E.

AU - Nizovtsev, Anton S.

AU - Lashchinskaya, Zoya N.

AU - Stepanov, Alexander G.

N1 - The authors acknowledge the financial support from the Russian Science Foundation (grant no. 21-73-10013). Computational resources for DFT calculations were provided by the Computational Center of Novosibirsk State University.

PY - 2024/3/7

Y1 - 2024/3/7

N2 - 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.

AB - 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.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85187338343&origin=inward&txGid=dc127060820074a70608fec2c2ba3ff3

UR - https://www.mendeley.com/catalogue/7f3cf85e-27ce-3966-b496-36e9ae76dd11/

U2 - 10.1021/acs.inorgchem.3c04611

DO - 10.1021/acs.inorgchem.3c04611

M3 - Article

C2 - 38453174

VL - 63

SP - 5083

EP - 5097

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 11

ER -