Xiu-hui Lu, Yong-qing Li, Yue-hua Xu, Jun-feng Han, Le-yi Shi. Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde[J]. Chinese Journal of Chemical Physics , 2010, 23(3): 287-292. doi: 10.1088/1674-0068/23/03/287-292
Citation: Xiu-hui Lu, Yong-qing Li, Yue-hua Xu, Jun-feng Han, Le-yi Shi. Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde[J]. Chinese Journal of Chemical Physics , 2010, 23(3): 287-292. doi: 10.1088/1674-0068/23/03/287-292

Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

doi: 10.1088/1674-0068/23/03/287-292
  • Received Date: 2009-12-03
  • Mechanism of the cycloadditional reaction between singlet dichloro-germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry opti-mization, vibrational analysis and energies for the involved stationary points on the poten-tial energy surface. From the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dom-inant reaction pathways, going with the formation of two side products (INT3 and INT4), simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-transfer product P2 via transition state TS2,with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.
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Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

doi: 10.1088/1674-0068/23/03/287-292

Abstract: Mechanism of the cycloadditional reaction between singlet dichloro-germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry opti-mization, vibrational analysis and energies for the involved stationary points on the poten-tial energy surface. From the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dom-inant reaction pathways, going with the formation of two side products (INT3 and INT4), simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-transfer product P2 via transition state TS2,with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.

Xiu-hui Lu, Yong-qing Li, Yue-hua Xu, Jun-feng Han, Le-yi Shi. Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde[J]. Chinese Journal of Chemical Physics , 2010, 23(3): 287-292. doi: 10.1088/1674-0068/23/03/287-292
Citation: Xiu-hui Lu, Yong-qing Li, Yue-hua Xu, Jun-feng Han, Le-yi Shi. Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde[J]. Chinese Journal of Chemical Physics , 2010, 23(3): 287-292. doi: 10.1088/1674-0068/23/03/287-292

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