Tan Xiaojun, Li Ping, Wang Dangsheng. Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde[J]. Chinese Journal of Chemical Physics , 2005, 18(6): 913-917. doi: 10.1088/1674-0068/18/6/913-917
Citation: Tan Xiaojun, Li Ping, Wang Dangsheng. Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde[J]. Chinese Journal of Chemical Physics , 2005, 18(6): 913-917. doi: 10.1088/1674-0068/18/6/913-917

Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde

doi: 10.1088/1674-0068/18/6/913-917
Funds:  Project supported by the Natural Science Foundation of Shandong Province (Y2002B05).
  • Received Date: 2004-12-26
  • The mechanisms of the cycloaddition reaction of singlet GeX2(X=F,Cl) with formaldehyde was studied employing the HF/6-311+G theory. The electron-correlation corrections have been further considered by the fourth-order Muller-Plesset perturbation theory (MP4SDTQ/6-311+G). The results show that this reaction proceeds in two steps: ① Difluorogemylene and formaldehyde form an intermediate complex, which is a barrierless exothermal reaction; ② the intermediate complex isomerizes to form the product, which is a rate-control step in the whole reaction. In the second step, the calculated barrier heights are 216.7 and 196.4 kJ/mol before and after considering electron-correlation effects. Compared with that of the cycloaddition reaction of difluorosilylene with formaldehyde, the cycloaddition reaction of difluorogemylene with formaldehyde is relatively slow, whereas the cycloaddition reaction of dichlorogemylene with formaldehyde can be comparable in speed.
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Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde

doi: 10.1088/1674-0068/18/6/913-917
Funds:  Project supported by the Natural Science Foundation of Shandong Province (Y2002B05).

Abstract: The mechanisms of the cycloaddition reaction of singlet GeX2(X=F,Cl) with formaldehyde was studied employing the HF/6-311+G theory. The electron-correlation corrections have been further considered by the fourth-order Muller-Plesset perturbation theory (MP4SDTQ/6-311+G). The results show that this reaction proceeds in two steps: ① Difluorogemylene and formaldehyde form an intermediate complex, which is a barrierless exothermal reaction; ② the intermediate complex isomerizes to form the product, which is a rate-control step in the whole reaction. In the second step, the calculated barrier heights are 216.7 and 196.4 kJ/mol before and after considering electron-correlation effects. Compared with that of the cycloaddition reaction of difluorosilylene with formaldehyde, the cycloaddition reaction of difluorogemylene with formaldehyde is relatively slow, whereas the cycloaddition reaction of dichlorogemylene with formaldehyde can be comparable in speed.

Tan Xiaojun, Li Ping, Wang Dangsheng. Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde[J]. Chinese Journal of Chemical Physics , 2005, 18(6): 913-917. doi: 10.1088/1674-0068/18/6/913-917
Citation: Tan Xiaojun, Li Ping, Wang Dangsheng. Theoretical Study on Mechanism of Cycloaddition Reaction of GeX2(X=F,Cl) with Formaldehyde[J]. Chinese Journal of Chemical Physics , 2005, 18(6): 913-917. doi: 10.1088/1674-0068/18/6/913-917

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