Citation: YAN Bing-Fei, LI Wen-Zuo, XIAO Cui-Ping, LI Qing-Zhong, CHENG Jian-Bo. Mechanism of Insertion Reactions between Silylenoid H₂SiLiF and GeH₃R (R=F, OH, NH₂): a Theoretical Study[J]. Chinese Journal of Structural Chemistry, ;2015, 34(7): 1004-1012. doi: 10.14102/j.cnki.0254-5861.2011-0636 shu

Mechanism of Insertion Reactions between Silylenoid H₂SiLiF and GeH₃R (R=F, OH, NH₂): a Theoretical Study

1.
The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China

Received Date: 13 January 2015
Available Online: 5 May 2015
Fund Project: This project was supported by the National Natural Science Foundation Committee of China (No. 21103145) (No. 21103145) the Fund for Doctor of Yantai University (No. HY05B30) (No. ZR2009BQ006) and the Special Foundation of Youth Academic Backbone of Yantai University. Professor CHENG acknowledges support by the Open fund (sklssm201418) of the State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Yan B. F. acknowledges the Graduate Innovation Foundation of Yantai University, GIFYTU (No. HY05B30)

Theoretical investigations on the insertion reaction mechanisms of three-membered-ring silylenoid H₂SiLiF with GeH₃R (R=F, OH, NH₂) have been systematically carried out by combined density functional theory (DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with GeH₃R proceed in a concerted manner, forming H₂RSi-GeH₃ and LiF. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 kJ/mol, and the reaction energies for the three reactions are -127.05, -116.91, and -103.31 kJ/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH₃-F> GeH₃-OH> GeH₃-NH₂. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation.
- insertion reactions,
- silylenoid H₂SiLiF,
- GeH₃R (R=F,
- OH,
- NH₂),
- DFT
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