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 reactivity of persulfide (RSS^–), perselenide (RSeSe^–), thioselenide (RSSe^–), and selenosulfide (RSeS^–) anions. The isolated chalcogenides do not rely on steric protection for stability and have steric profiles analogous to cysteine (Cys). Simple reduction of S₈ or Se by potassium benzyl thiolate (KSBn) or selenolate (KSeBn) in the presence of 18-crown-6 afforded [K(18-crown-6)][BnSS] (1), [K(18-crown-6)][BnSeSe] (2), [K(18-crown-6][BnSSe] (3), and [K(18-crown-6][BnSeS] (4). The chemical structure of each dichalcogenide was confirmed by X-ray crystallography and solution-state ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. To advance our understanding of the reactivity of these species, we demonstrated that reduction of 1–4 by PPh₃ readily generates E═PPh₃ (E: S, Se), and reduction of 1, 3, and 4 by DTT readily produces HE^–/H₂E. Furthermore, 1–4 react with CN^– to produce ECN^–, which is consistent with the detoxifying effects of dichalcogenide intermediates in the Rhodanese enzyme. Taken together, this work provides new insights into the inherent structural and reactivity characteristics of dichalcogenides relevant to biology and advances our understanding of the fundamental properties of these reactive anions.

中文翻译：

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驯服二硫化物：难以捉摸的过硒化物、过硫化物、硫代硒化物和硒硫醚阴离子的分离、表征和反应性

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] ( 4 )。每种二硫属化物的化学结构通过以下方式确认X 射线晶体学和溶液态¹ H、¹³ C 和⁷⁷ Se NMR 光谱。为了加深我们对这些物质反应性的理解，我们证明通过 PPh _3还原1 – 4很容易生成 E=PPh ₃ (E ：S、Se)，并减少1，3、4通过DTT很容易生成HE ^- /H ₂ E。此外，1 - 4与CN ^-反应生成ECN ^- ，这与Rhodanese酶中二硫属化物中间体的解毒作用一致。总而言之，这项工作为与生物学相关的二硫属化物的固有结构和反应性特征提供了新的见解，并增进了我们对这些反应性阴离子基本性质的理解。