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Counter-ion effect in the nucleophilic substitution reactions at silicon: a G2M(+) level theoretical investigation

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Abstract

Three identity nucleophilic substitution reactions at tetracoordinated silicon atom with inversion and retention pathways: Nu +  SiH3Cl → Nu +  SiH3Cl[Nu =  (1)Cl−, (2) LiCl, and (3) (LiCl)2], are investigated using the G2M(+) theory. Our results show that changing the nucleophile can shift the mechanism (favorable pathway), stepwise from a single-well PES for reaction 1, via a double-well PES for reaction 2, to a triple-well PES for reaction 3, indicating the importance of steric and electronic effects on the SN2@Si.

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Authors and Affiliations

  1. Faculty of Chemistry and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610064, People’s Republic of China

    Yi Ren & Xin Wang

  2. Department of Chemistry, National Tsing Hua University, Hsinchu, 30013, Taiwan, Republic of China

    San-Yan Chu

  3. Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, People’s Republic of China

    Ning-Bew Wong

Authors
  1. Yi Ren
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  2. Xin Wang
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  3. San-Yan Chu
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  4. Ning-Bew Wong
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Correspondence to Yi Ren or San-Yan Chu.

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Ren, Y., Wang, X., Chu, SY. et al. Counter-ion effect in the nucleophilic substitution reactions at silicon: a G2M(+) level theoretical investigation. Theor Chem Account 119, 407–411 (2008). https://doi.org/10.1007/s00214-007-0386-3

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  • DOI: https://doi.org/10.1007/s00214-007-0386-3

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