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

Date

2012-03-29

Author

Bozkaya, Ugur
Özkan, İlker

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

142
views

0
downloads

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

Suggestions

OpenMETU
Core

Thermal Aromatizations of 2-Vinylmethylenecyclopropane and 3-Vinylcyclobutene Bozkaya, Ugur; Özkan, İlker (2012-07-06) A comprehensive theoretical investigation of thermal rearrangements of 2-vinylmethylenecyclopropane and 3-vinylcyclobutene is carried out employing density functional theory and high level ab initio methods, such as the complete active space self-consistent field, multi-reference second-order Moller-Plesset perturbation theory, and coupled-cluster singles and doubles with perturbative triples. In all computations, Pople's polarized triple-zeta split valence basis set, 6-311G(d,p), is utilized. The potential...
Thermal denitrogenation of 7-isopropylidene-2,3-diaza-norbornene: formation of substituted 3-methylene-(1,4)-pentadienes Bozkaya, Ugur; Özkan, İlker (2012-01-01) A theoretical study of the thermal denitrogenation of 7-isopropylidene-2,3-diaza-norbornene is carried out by employing density functional theory and high level ab initio methods, such as the complete active space self-consistent field, multi-reference second-order Moller-Plesset perturbation theory, and coupled-cluster singles and doubles with perturbative triples. In all computations Pople's polarized triple-zeta split valence basis set, 6-311G(d,p), is utilized. The potential energy surface for the relev...
Theoretical Study of Thermal Rearrangements of 1-Hexen-5-yne, 1,2,5-Hexatriene, and 2-Methylenebicyclo[2.1.0]pentane Bozkaya, Ugur; Özkan, İlker (2012-03-02) In this research, a comprehensive theoretical investigation of the thermal rearrangements of 1-hexen-5-yne, 1,2,5-hexatriene, and 2-methylenebicyclo[2.1.0]pentane is carried out employing density functional theory (DFT) 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)]. The potential energy surface (PES) for the ...
Catalytic partial oxidation of propylene on metal surfaces by means of quantum chemical methods Kızılkaya, Ali Can; Önal, Işık; Department of Chemical Engineering (2010) Direct, gas phase propylene epoxidation reactions are carried out on model slabs representing Ru-Cu(111) bimetallic and Cu(111) metallic catalyst surfaces with periodic Density Functional Theory (DFT) calculations. Ru-Cu(111) surface is modelled as a Cu(111) monolayer totally covering the surface of Ru(0001) surface underneath. The catalytic activity is evaluated following the generally accepted oxametallacycle mechanism. It is shown that the Ru-Cu(111) surface has a lower energy barrier (0.48 eV) for the s...
Quantum chemical simulation of nitric oxide reduction by ammonia (scr reaction) on v2o5 / tio2 catalyst surface Soyer, Sezen; Önal, Işıl; Department of Chemical Engineering (2005) The reaction mechanism for the selective catalytic reduction (SCR) of nitric oxide by ammonia on (010) V2O5 surface represented by a V2O9H8 cluster was simulated by density functional theory (DFT) calculations. The computations indicated that SCR reaction consisted of three main parts. In the first part ammonia activation on Brønsted acidic V-OH site as NH4+ species by a nonactivated process takes place. The second part includes the interaction of NO with pre-adsorbed NH4 + species to eventually form nitros...

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.