Theoretical study of the ring expansion reaction mechanism of cyclopropenylidene with azetidine

Tan, Xiaojun, Wang, Weihua, Sun, Qiao, Jing, Ying and Li, Ping (2014) Theoretical study of the ring expansion reaction mechanism of cyclopropenylidene with azetidine. Journal of Molecular Modeling, 20 3: 1-7. doi:10.1007/s00894-014-2088-9


Author Tan, Xiaojun
Wang, Weihua
Sun, Qiao
Jing, Ying
Li, Ping
Title Theoretical study of the ring expansion reaction mechanism of cyclopropenylidene with azetidine
Journal name Journal of Molecular Modeling   Check publisher's open access policy
ISSN 1610-2940
0948-5023
Publication date 2014-03
Year available 2014
Sub-type Article (original research)
DOI 10.1007/s00894-014-2088-9
Open Access Status
Volume 20
Issue 3
Start page 1
End page 7
Total pages 7
Place of publication Heidelberg, Germany
Publisher Springer
Collection year 2015
Language eng
Formatted abstract
The mechanism for the ring expansion reaction between cyclopropenylidene and azetidine was systematically investigated employing second-order Møller–Plesset perturbation theory (MP2) in order to better understand the reactivity of cyclopropenylidene with the four-membered ring compound azetidine. Geometry optimizations and vibrational analyses were performed for the stationary points on the potential energy surfaces of the system. The results of our calculations show that cyclopropenylidene can insert into azetidine at its C–N or C–C bond. From a kinetic viewpoint, it is easier for cyclopropenylidene to insert into the C–N bond of azetidine than into the C–C bond. During the first insertion step and the second ring-opening step, it forms spiro and carbene intermediates, respectively. In the following two H-transfer steps, the carbene intermediate forms allenes and alkynes, respectively, as products. From a thermodynamic perspective, allenes are the dominant product because the reaction is exothermic by 373.4 kJ/mol−1.
Keyword Cyclopropenylidene
Azetidine
Reaction mechanism
MP2 method
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Article no.: 2088

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
Australian Institute for Bioengineering and Nanotechnology Publications
 
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