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      저자 : Jinping Xing (검색결과 2 건)
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        Theoretical Studies on the Alkylidene Silylenoid H<sub>2</sub>C = SiLiF and Its Insertion Reaction with R-H (R = F, OH, NH<sub>2</sub>)

        Tan, Xiaojun,Wang, Weihua,Li, Ping,Li, Qingyan,Cheng, Lei,Wang, Shufen,Cai, Weiwang,Xing, Jinping Korean Chemical Society 2010 Bulletin of the Korean Chemical Society Vol.31 No.5

        The geometries and isomerization of the alkylidene silylenoid $H_2C$ = SiLiF as well as its insertion reactions with R-H (R = F, OH, $NH_2$) have been systematically investigated at the B3LYP/6-311+$G^*$ level of theory. The potential barriers of the three insertion reactions are 97.5, 103.3, and 126.1 kJ/mol, respectively. Here, all the mechanisms of the three reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted silylene ($H_2C$ = SiHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the three reactions are -36.4, -24.3, and 3.7 kJ/mol, respectively. Compared with the insertion reaction of $H_2C$ = Si: and R-H (R = F, OH and $NH_2$), the introduction of LiF makes the insertion reaction occur more easily. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the three insertion reactions should be as follows: H-F > H-OH > H-$NH_2$.

      • KCI등재

        Theoretical Studies on the Alkylidene Silylenoid H2C = SiLiF and Its Insertion Reaction with R-H (R = F, OH, NH2)

        Xiaojun Tan,Weihua Wang,Ping Li,Qingyan Li,Lei Cheng,Shufen Wang,Weiwang Cai,Jinping Xing 대한화학회 2010 Bulletin of the Korean Chemical Society Vol.31 No.5

        The geometries and isomerization of the alkylidene silylenoid H2C = SiLiF as well as its insertion reactions with R-H (R = F, OH, NH2) have been systematically investigated at the B3LYP/6-311+G* level of theory. The potential barriers of the three insertion reactions are 97.5, 103.3, and 126.1 kJ/mol, respectively. Here, all the mechanisms of the three reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted silylene (H2C = SiHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the three reactions are ‒36.4, ‒24.3, and 3.7kJ/mol, respectively. Compared with the insertion reaction of H2C = Si: and R-H (R = F, OH and NH2), the introduction of LiF makes the insertion reaction occur more easily. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the three insertion reactions should be as follows: H-F > H-OH > H-NH2.

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