Ab initio studies on mechanisms of cycloaddition reaction between dichloro-vinylidene and ethylene |
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Authors: | Xiuhui Lu and Yixuan Wang |
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Affiliation: | aSchool of Chemistry and Chemical Engineering, Jinan University, Jinan, Shandong 250002, People's Republic of China bDepartment of Chemical Engineering, Texas A and M University, TAMU 3122, College Station, TX 77843, USA |
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Abstract: | Mechanisms of cycloaddition reaction between singlet dichloro-vinylidene (R1) and ethylene (R2) have been investigated with MP2 and B3LYP /6-31G* methods, including geometry optimization, vibrational analysis, and energy for the involved stationary points on the potential energy surface. CCSD(T)/6-31G* single point calculations are also applied to the geometries from both methods. CCSD(T) relative energies for the stationary points predicted by MP2 and B3LYP are in a very good agreement. Three reaction pathways are located. Along the first one, one intermediate (INT1) is firstly generated, which then rearranges into a three-membered ring compound (P1) via a small barrier of 5.4 kJ/mol; the other two paths share the other intermediate (INT2), which isomerizes into two four-membered ring compounds (P2 and P3) via a chlorine and a hydrogen transfer, respectively. The barriers of the latter two paths are significantly higher by approximately 25 kJ/mol than that of the former (27.2 and 28.8 vs 5.4 kJ/mol), the major reaction is therefore the formation of P1. |
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Keywords: | Vibrational analysis Potential energy surface Carbene |
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