Reactions of an Isolable Dialkylstannylene with Carbon Disulfide and Related Heterocumulenes

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• 作者：Chenting Yan ; Zheng Xu ; Xu-Qiong Xiao ; Zhifang Li ; Qiong Lu ; Guoqiao Lai ; Mitsuo Kira
• 刊名：Organometallics
• 出版年：2016
• 出版时间：May 9, 2016
• 年：2016
• 卷：35
• 期：9
• 页码：1323-1328
• 全文大小：412K
• 年卷期：0
• ISSN：1520-6041

文摘

The reaction of isolable dialkylstannylene 1 with an excess amount of CS₂ produces an isomeric mixture of 3,3′-distanna-2,2′,4,4′-tetrathiabicyclobutylidene 8 and 3,7-distanna-2,4,6,8-tetrathiabicyclo[3.3.0]oct-1(5)-ene 9 with a ratio depending on the reaction conditions. Compounds 8 and 9 are separated by column chromatography and characterized by NMR spectroscopy and X-ray crystallography. Detailed investigation of the reaction has revealed that the initial product is 8, which isomerizes to 9 irreversibly under the catalytic influence of 1 as a Lewis acid. The above view is supported by the theoretical DFT calculations. Treatment of 1 with ArN═C═O [Ar = 2,6-iPr₂C₆H₃] affords the corresponding carbamoyl(hydroxyl)stannane 11 via the hydrolysis of the corresponding silaaziridinone formed by the [1 + 2] cycloaddition reaction of 1 with the N═C double bond of the isocyanate. Stannylene 1 reacts with ArN═C═S, giving a mixture of complex products, while 1 does not react with CO₂.