Taming the Dichalcogenides: Isolation, Characterization, and Reactivity of Elusive Perselenide, Persulfide, Thioselenide, and Selenosulfide Anions
作者:Keyan Li、Lev N. Zakharov、Michael D. Pluth
DOI:10.1021/jacs.3c03766
日期:2023.6.21
Reactive sulfur species (RSS) and reactive selenium species (RSeS) play integral roles in hydrogen sulfide (H2S) and hydrogen selenide (H2Se) biological signaling pathways, and dichalcogenide anions are proposed transient intermediates that facilitate a variety of biochemical transformations. Herein we report the selective synthesis, isolation, spectroscopic and structural characterization, and fundamental
活性硫(RSS)和活性硒(RSeS)在硫化氢(H 2 S)和硒化氢(H 2 Se)生物信号传导途径中发挥着不可或缺的作用,并且二硫属化物阴离子被认为是促进各种生化转化的瞬时中间体。在此,我们报告了过硫化物 (RSS – )、过硒化物 (RSeSe – )、硫代硒化物 (RSSe – ) 和硒硫醚 (RSeS – ) 阴离子的选择性合成、分离、光谱和结构表征以及基本反应性。分离的硫属化物不依赖于空间保护来保持稳定性,并且具有类似于半胱氨酸(Cys)的空间分布。S 8的简单还原或 Se 在 18-crown-6 存在下通过苄基硫醇钾 (KSBn) 或硒醇钾 (KSeBn) 进行反应,得到 [K(18-crown-6)][BnSS] ( 1 ), [K(18-crown- 6 ) ][BnSeSe] ( 2 )、[K(18-crown-6][BnSSe] ( 3 ) 和 [K(18-crown-6][BnSeS]