Ab initio study on the mechanism of forming a silapolycyclic compound between methylenesilylene and ethene

作者：Lu Xiuhui^*; Che Xin; Yu Haibin; Xiang Pingping; Xu Yuehua

来源：Journal of Molecular Structure (Theochem), 2007, 821(1-3): 53-57.

DOI：10.1016/j.theochem.2007.06.024

• methylenesilylene
• cycloaddition reaction
• potential energy surface
• CCSD(T)//MP2/6-31G*method

The mechanism of the cycloaddition reaction of forming a silapolycyclic compound between singlet methylenesilylene and ethene has been investigated with the MP2/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that, reaction (3) is the dominant channel of cycloaddition reaction between singlet methylenesilylene and ethene. This reaction consists of four steps: (1) the two reactants first form a three-membered ring intermediate TNT through a barrier-free exothermic reaction of 13.3 kJ mol(-1); (II) TNT then isomerizes to a four-membered ring product P2 via the transition state TS2 with an energy barrier of 32.0 kJ mol(-1); (III) P2 further reacts with ethene(R2) to form a silapolycyclic intermediate INT3, which is also a barrier-free exothermic reaction of 11.8 kJ mol(-1); (IV) INT3 isomerizes to a silapolycyclic compound P3 via the transition state TS3 with an energy barrier of 1.5 kJ mol(-1). This reaction has quite excellent selectivity.

• 出版日期2007-11-1
• 单位暨南大学