Ab initio study on the mechanism of forming a silapolycyclic compound between silylidene and formaldehyde |
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Authors: | Xiuhui Lu Haibin Yu Yuehua Xu Pingping Xiang Yandi Liu |
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Institution: | aSchool of Chemistry and Chemical Engineering, Jinan University, Jinan, Shandong 250022, People's Republic of China |
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Abstract: | The mechanism of the cycloaddition reaction of forming a silapolycyclic compound between singlet silylidene and formaldehyde has been investigated with 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 CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the cycloaddition reaction process of forming the silapolycyclic compound (P2) for this reaction consists of four steps: (I) the two reactants first form a semi-cyclic intermediate INT1a through a barrier-free exothermic reaction of 32.5 kJ mol?1; (II) this intermediate then isomerizes to an active four-membered ring intermediate INT1 via a transition state TS1a with an energy barrier of 30.8 kJ mol?1; (III) INT1 further reacts with formaldehyde to form an intermediate INT2, which is also a barrier-free exothermic reaction of 30.1 kJ mol?1; (IV) INT2 isomerizes to a silapolycyclic compound P2 via a transition state TS2 with a barrier of 50.6 kJ mol?1. Comparing this reaction path with other competitive reaction paths, we can see that this cycloaddition reaction has an excellent selectivity. |
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Keywords: | Silylidene Cycloaddition reaction Potential energy surface |
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