Synthesis, Characterization, and Reactivity of Metalla‐Chalcogenirenium Compounds †
Synthesis, Characterization, and Reactivity of Metalla‐Chalcogenirenium Compounds †
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Metalla – 硫族鎓化合物的合成、表征和反应性 –
DOI：
10.1002/cjoc.202000745
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Haiping Xia
中科院分区：
文献类型：
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作者：
Ming Luo;Yapeng Cai;Xinlei Lin;Lipeng Long;Hong Zhang;Haiping Xia
主要观察和结论硫属阳离子，具有不饱和的三元有机环，是有限的，但已知可以从具有庞大的供电子基团的炔合成。通过环状金属-碳炔络合物-金属戊炔与PhSCl、PhSeCl或PhTeCl的反应，已经合成了金属-硫属化合物作为稳定的化合物。由于三元金属杂环中的高应变，金属硫属阳离子很容易与碱或氯离子反应。这些反应提供了一系列前所未有的具有完整M=C键的硫属阳离子。芳香性的内在稳定效应通过密度泛函计算得到了进一步的解释。
Main observation and conclusionChalcogenirenium cations, featuring an unsaturated three‐membered organic ring, are limited but known to be synthesizable from alkynes with bulky electron‐donating groups. Metalla‐chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal‐carbyne complex—metallapentalyne with PhSCl, PhSeCl or PhTeCl. As a result of the high strain in the three‐membered metallacycles, the metalla‐chalcogenirenium cations react readily with the base or chloride ions. These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds. The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.