Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene
A quantum chemical method was employed to investigate the mechanism of dimerization reactions of alkyl ketene. All the geometric configurations of the stationary points on the reactions path were optimized with Gaussian03 employing density functional theory at the B3LYP/6-311G++(d, p) level by energ...
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| Format: | Article |
| Language: | English |
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Wiley
2013-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2013/481586 |
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| author | Zhiguo Zhang Guoneng Li Guilin Hu Yaoyu Sun |
| author_facet | Zhiguo Zhang Guoneng Li Guilin Hu Yaoyu Sun |
| author_sort | Zhiguo Zhang |
| collection | DOAJ |
| description | A quantum chemical method was employed to investigate the mechanism of dimerization reactions of alkyl ketene. All the geometric configurations of the stationary points on the reactions path were optimized with Gaussian03 employing density functional theory at the B3LYP/6-311G++(d, p) level by energy gradient technique. The transition states were also investigated through synchronous transit method, and its reasonability was confirmed by using frequency analysis and intrinsic reaction coordinate analysis. The results can be summed up as follows: according to the frontier orbital theory, the dimerization reaction (3) to generate four-membered carbon cyclic product P3 is forbidden. Two different dimerization processes of alkyl ketene are all concerted but nonsynchronous, taking place through twisted four-membered cyclic transition states. The activation energies were calculated to be 34.54 and 61.73 kJ/mol, respectively for the two ketene dimerization processes. Calculation results satisfactorily explained the experimental facts. |
| format | Article |
| id | doaj-art-75918a8b43124e34a31ef55d5a170e08 |
| institution | Kabale University |
| issn | 2090-9063 2090-9071 |
| language | English |
| publishDate | 2013-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Chemistry |
| spelling | doaj-art-75918a8b43124e34a31ef55d5a170e082025-02-03T01:32:15ZengWileyJournal of Chemistry2090-90632090-90712013-01-01201310.1155/2013/481586481586Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl KeteneZhiguo Zhang0Guoneng Li1Guilin Hu2Yaoyu Sun3School of Light Industry, Zhejiang University of Science and Technology, Liuhe Road No. 318, Hangzhou, Zhejiang 310023, ChinaSchool of Light Industry, Zhejiang University of Science and Technology, Liuhe Road No. 318, Hangzhou, Zhejiang 310023, ChinaSchool of Light Industry, Zhejiang University of Science and Technology, Liuhe Road No. 318, Hangzhou, Zhejiang 310023, ChinaSchool of Light Industry, Zhejiang University of Science and Technology, Liuhe Road No. 318, Hangzhou, Zhejiang 310023, ChinaA quantum chemical method was employed to investigate the mechanism of dimerization reactions of alkyl ketene. All the geometric configurations of the stationary points on the reactions path were optimized with Gaussian03 employing density functional theory at the B3LYP/6-311G++(d, p) level by energy gradient technique. The transition states were also investigated through synchronous transit method, and its reasonability was confirmed by using frequency analysis and intrinsic reaction coordinate analysis. The results can be summed up as follows: according to the frontier orbital theory, the dimerization reaction (3) to generate four-membered carbon cyclic product P3 is forbidden. Two different dimerization processes of alkyl ketene are all concerted but nonsynchronous, taking place through twisted four-membered cyclic transition states. The activation energies were calculated to be 34.54 and 61.73 kJ/mol, respectively for the two ketene dimerization processes. Calculation results satisfactorily explained the experimental facts.http://dx.doi.org/10.1155/2013/481586 |
| spellingShingle | Zhiguo Zhang Guoneng Li Guilin Hu Yaoyu Sun Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene Journal of Chemistry |
| title | Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene |
| title_full | Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene |
| title_fullStr | Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene |
| title_full_unstemmed | Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene |
| title_short | Theoretical Research on the Mechanism of the Dimerization Reactions of Alkyl Ketene |
| title_sort | theoretical research on the mechanism of the dimerization reactions of alkyl ketene |
| url | http://dx.doi.org/10.1155/2013/481586 |
| work_keys_str_mv | AT zhiguozhang theoreticalresearchonthemechanismofthedimerizationreactionsofalkylketene AT guonengli theoreticalresearchonthemechanismofthedimerizationreactionsofalkylketene AT guilinhu theoreticalresearchonthemechanismofthedimerizationreactionsofalkylketene AT yaoyusun theoreticalresearchonthemechanismofthedimerizationreactionsofalkylketene |