Protonated Methylcyclopropane is an Intermediate Providing Complete 13C-Label Scrambling at C4 Olefin Isomerization in Zeolite | Sciact - CRIS-system of Boreskov Institute of Catalysis

Protonated Methylcyclopropane is an Intermediate Providing Complete 13C-Label Scrambling at C4 Olefin Isomerization in Zeolite Full article

Journal

Chem Catalysis
ISSN: 2667-1093

Output data

Year: 2023, Volume: 3, Number: 2, Article number : 100503, Pages count : 15 DOI: 10.1016/j.checat.2022.100503

Tags

zeolite; carbocations; three-center two-electron; monomolecular mechanism; bimolecular mechanism; reaction intermediate; protonated methylcyclopropane; skeletal rearrangement; confinement effect

Authors

Chen Wei ¹ , Huang Mengdi ¹ , Yi Xianfeng ¹ , Hui Yu ⁶ , Gao Pan ² , Hou Guangjin ² , Stepanov Alexander G. ⁴ , Qin Yucai ⁶ , Song Lijuan ⁶ , Liu Shang-Bin ⁵ , Chen Zhongfang ³ , Zheng Anmin ¹

Affiliations

1	State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, P.R. China
2	State Key Laboratory of Catalysis, National Laboratory for Clean Energy, 2011-Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R. China
3	Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, San Juan, PR 00931, USA
4	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, 630090 Novosibirsk, Russia
5	Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan
6	Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Petrochemical University, Fushun 113001, China

Funding (10)

1	National Natural Science Foundation of China	22125304
2	National Natural Science Foundation of China	22032005
3	National Natural Science Foundation of China	22002174
4	National Natural Science Foundation of China	21902180
5	National Natural Science Foundation of China	21991092
6	National Natural Science Foundation of China	21773230
7	National Natural Science Foundation of China	91945302
8	European Commission	2021YFA1502600
9	European Commission	2022YFE0116000
10	National Science Foundation	HRD-1736093

Carbocations play crucial roles during catalytic reactions by dictating the reaction pathways and genuine mechanisms, but the instability of carbocations prevents thorough observations. The stabilization of carbocations would greatly help us gain a deep understanding of the reaction mechanisms. By means of ab initio molecular dynamics (AIMD) simulations and an in situ experimental approach, a complete scrambling of 13C-labeled C4= products was observed during the isomerization reaction in the H-ZSM-5 zeolite at room temperature, and the corner-protonated methylcyclopropanes (as a non-classical carbocation) featuring the three-center two-electron (3c–2e) bonds were confirmed to be the highly active metastable intermediates of C4 isomerization. Our results not only uncover the nature of facile C shift in carbocations during zeolite-catalyzed reactions but also bring some fundamental understandings to carbocation chemistry in a zeolite confined environment.

Chen W. , Huang M. , Yi X. , Hui Y. , Gao P. , Hou G. , Stepanov A.G. , Qin Y. , Song L. , Liu S-B. , Chen Z. , Zheng A.
Protonated Methylcyclopropane is an Intermediate Providing Complete 13C-Label Scrambling at C4 Olefin Isomerization in Zeolite
Chem Catalysis. 2023. V.3. N2. 100503 :1-15. DOI: 10.1016/j.checat.2022.100503 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Oct 17, 2022
Accepted:	Dec 29, 2022
Published online:	Jan 24, 2023
Published print:	Feb 16, 2023

Web of science:	WOS:000943989800001
Scopus:	2-s2.0-85148008072
Elibrary:	54903593
Chemical Abstracts:	2023:379363
Chemical Abstracts (print):	182:423439
OpenAlex:	W4317897803

DB	Citing
Web of science	5
Scopus	5
OpenAlex	3
Elibrary	3