NDLI: Ionic $S_{N}i-Si$ Nucleophilic Substitution in N-Methylaniline-Induced Si−Si Bond Cleavages of $Si_{2}Cl_{6}$

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Ionic $S_{N}i-Si$ Nucleophilic Substitution in N-Methylaniline-Induced Si−Si Bond Cleavages of $Si_{2}Cl_{6}$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Zhang, Jie Zhang, Lin Zuo, Yujing Feng, Shengyu Lee, Myong Euy Xie, Ju
Description	Author Affiliation: Zhang J ( Key Laboratory of Special Functional Aggregated Materials and, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P.R. China.); Xie J ( College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, P.R. China.); Lee ME ( Department of Chemistry and Medical Chemistry, College of Science and Technology, Research and, Education Center for Advanced Silicon Materials, Yonsei University, Wonju, Gangwon-do, 220-710, South Korea.); Zhang L ( Key Laboratory of Special Functional Aggregated Materials and, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P.R. China.); Zuo Y ( Key Laboratory of Special Functional Aggregated Materials and, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P.R. China.); Feng S ( Key Laboratory of Special Functional Aggregated Materials and, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P.R. China.)
Abstract	N-Methylaniline-induced Si−Si bond cleavage of $Si_{2}Cl_{6}$ has been theoretically studied. All calculations were performed by using DFT at the MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) levels. An ionic $S_{N}i-Si$ nucleophilic substitution mechanism, which is a newly found nucleophilic substitution in silicon-containing compounds, is proposed in the N-methylaniline-induced Si−Si bond cleavage in $Si_{2}Cl_{6}.$ Unlike general $S_{N}i-Si$ nucleophilic substitutions that go through a pentacoordinated silicon transition state, ionic nucleophilic substitution goes through a tetracoordinated silicon transition state, in which the Si−Si bond is broken and siliconium ions are formed. Special cleavage of the Si−Si bond is presumably due to the good bonding strength between Si and N atoms, which leads to polarization of the Si−Si bond and eventually to heterolytic cleavage. Calculation results show that, in excess N-methylaniline, the final products of the reaction, including $(NMePh)_{3−n}SiHCl_{n}$ (n=0–2) and $(NMePh)_{4−n}SiCl_{n}$ (n=2–3), are the Si−Si cleavage products of $Si_{2}Cl_{6}$ and the corresponding amination products of the former. The ionic $S_{N}i-Si$ nucleophilic substitution mechanism can also be employed to describe the amination of chlorosilane by N-methylaniline. The suggested mechanisms are consistent with experimental data.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	14
Volume Number	22
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2016-03-24
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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