Theoretical study on the stability of osmasilabenzynes

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	Theoretical study on the stability of osmasilabenzynes
	Huang, Ying ; Wang, Xuerui ; An, Ke ; Fan, Jinglan ; Zhu, Jun ; Zhu J(朱军)
刊名	http://dx.doi.org/10.1039/c3dt53528b
	2014
关键词	ELECTRON LOCALIZATION FUNCTION INDEPENDENT CHEMICAL-SHIFTS RAY CRYSTAL-STRUCTURE POTENTIAL BASIS-SETS SILICON TRIPLE BOND MAIN-GROUP ELEMENTS TRANSITION-METAL SILYLENE COMPLEXES DENSITY FUNCTIONALS POLARIZATION FUNCTIONS
英文摘要	Chinese National Natural Science Foundation [21103142, 21133007]; National Basic Research Program of China [2011CB808504]; Program for New Century Excellent Talents in University [NCET-13-0511]; Program for Changjiang Scholars and Innovative Research Team in University; Fundamental Research Funds for Central Universities [2012121021]; Metallabenzyne has attracted considerable interest from theoreticians and experimentalists since its first isolation in 2001. However, metallasilabenzyne, formed by the replacement of the carbyne carbon with a silicon atom in metallabenzyne, has never been reported either theoretically or experimentally. Here we carry out density functional theory (DFT) calculations on this system for the first time. Our results reveal a polarized and weak Os-Si triple bond in osmasilabenzyne due to the reluctance of the silicon to participate in p bonding. The effect of the ligands, substituents on the metallacycle, and bases on the stability or aromaticity of osmasilabenzyne is also discussed in detail. Specifically, an antibonding interaction between the metal and metal-bonded carbon and silicon in the HOMO of osmasilabenzyne is identified. Thus electron-donating substituents on the metallacycle can destabilize it. Because the Os-Si triple bond in osmasilabenzyne is highly polarized, a Lewis base can stabilize it by coordinating to the silicon atom. All these findings could be helpful for experimentalists to realize the first metallasilabenzyne.
语种	英语
出版者	ROYAL SOC CHEMISTRY
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89445]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Huang, Ying,Wang, Xuerui,An, Ke,et al. Theoretical study on the stability of osmasilabenzynes[J]. http://dx.doi.org/10.1039/c3dt53528b,2014.
APA	Huang, Ying,Wang, Xuerui,An, Ke,Fan, Jinglan,Zhu, Jun,&朱军.(2014).Theoretical study on the stability of osmasilabenzynes.http://dx.doi.org/10.1039/c3dt53528b.
MLA	Huang, Ying,et al."Theoretical study on the stability of osmasilabenzynes".http://dx.doi.org/10.1039/c3dt53528b (2014).