Thermal Rearrangements of 1-Ethynyl-2-methylcyclopropane: A Computational Study

Date

2012-03-29

Author

Bozkaya, Ugur
Özkan, İlker

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In this research, a comprehensive theoretical investigation of the thermal rearrangements of 1-ethynyl-2-methylcyclopropane is carried out employing density functional theory (DFT), with the B3LYP functional, and high-level ab initio methods, such as the complete active space self-consistent field (CASSCF), multireference second-order Moller-Plesset perturbation theory (MRMP2), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. In all computations Pople's polarized triple-zeta split valence basis set, 6-311G(d,p), is utilized. The potential energy surface (PES) for the relevant system is explored to provide a theoretical account of the experiments by Hopf,(1-4) Ellis and Frey,(5) Huntsman et al.,(6) and Berson.(7) The computational results herein on the target system show that the thermal aromatization reaction does not proceed via conversion of 1,2,5-hexatriene (2) to 1,3,5-hexatriene (10a) as proposed by Hopf.(1-4) Indeed, the reaction proceeds via conversion of 5 and 6 to bicyclo[3.1.0]hexene (9) as suggested by Huntsman et al.(6)

Subject Keywords

Chemical structure, Chemical reactions, Energy, Activation energy, Mathematical methods

URI

https://hdl.handle.net/11511/31737

Journal

JOURNAL OF PHYSICAL CHEMISTRY A

DOI

https://doi.org/10.1021/jp3000575

Collections

Graduate School of Natural and Applied Sciences, Article

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Citation Formats

U. Bozkaya and İ. Özkan, “Thermal Rearrangements of 1-Ethynyl-2-methylcyclopropane: A Computational Study,” JOURNAL OF PHYSICAL CHEMISTRY A, pp. 3274–3281, 2012, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/31737.