Selective substitution of μ-SO₂^2– groups by either O^2– or Se^2– ions occurs upon heating the bioctahedral rhenium cluster complex K₆[Re₁₂CS₁₄(μ-SO₂)₃(CN)₆] in air atmosphere or in the presence of a Se source, respectively, manifesting the remarkable lability of SO₂^2– ligands bound to a transition-metal cluster. A series of compounds based on the new mixed-ligand anions, [Re₁₂CS₁₄(μ-O)₃(CN)₆]^6–, [Re₁₂CS₁₄(μ-Se)₃(CN)₆]^6–, and [Re₁₂CS₁₄(μ-O)₃(OH)₆]^6–, were isolated and their solid-state structures were elucidated by single-crystal X-ray diffraction analysis. Along with the previously reported μ-sulfide clusters, the new species constitute a series of rhenium anionic complexes with the common formula [Re₁₂CS₁₄(μ-Q)₃L₆]^6– (Q = O, S, Se, L = CN^–; Q = O, S, L = OH^–), within which the total charge and number of cluster valence electrons (CVEs) are constant. The article presents insights into the mechanistic and synthetic aspects of the substitution process, and it comprehensively discusses the influence of inner ligand environment on the structure, spectroscopic characteristics, and electrochemical behavior of the novel compounds.

中文翻译：

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在Re ₁₂生物四面体簇复合物中桥接SO ₂ ^2–配体的简便取代。

μ-SO的选择性取代_2个^2-通过或者是O基团^2-或Se ^2-离子发生在加热bioctahedral铼簇复合设备K ₆ [重₁₂ CS ₁₄（μ-SO ₂）₃（CN）₆ ]在空气气氛中或在有硒源的情况下，分别表明与过渡金属簇结合的SO ₂ ^2-配体具有显着的不稳定性。基于新的混合配体阴离子[Re ₁₂ CS ₁₄（μ-O）₃（CN）₆ ] ^6–，[Re ₁₂ CS_分离了[14（μ-Se）₃（CN）₆ ] ^6–和[Re ₁₂ CS ₁₄（μ-O）₃（OH）₆ ] ^6–，并通过单晶X阐明了它们的固态结构射线衍射分析。与先前报道的μ-硫化物簇一起，新物种构成了一系列of阴离子配合物，其通式为[Re ₁₂ CS ₁₄（μ-Q）₃ L ₆ ] ^6–（Q = O，S，Se，L = CN ^–； Q = O，S，L = OH ^–），其中总电荷和簇价电子（CVE）的数量是恒定的。本文介绍了取代过程的机理和合成方面的见解，并全面讨论了内部配体环境对新型化合物的结构，光谱特征和电化学行为的影响。