The high-temperature (∼180 °C) reaction between free-base meso-triarylcorroles and Re₂(CO)₁₀, followed by exposure to PCl₃ and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67–76% yields. The use of shorter reaction times, lower temperatures (∼130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO–LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV–vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re–S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists’ view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium’s oxophilicity and thiophilicity are essentially evenly balanced.

中文翻译：

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硫化铼和二硫醇甲醛：对亲铜性的反思


游离碱内消旋三芳基甲苯与 Re₂（CO）₁₀ 之间的高温 （∼180 °C） 反应，然后暴露于 PCl₃ 和硫醇（或元素硫），得到铼-硫化物 （ReS） 甲苯，产率为 67-76%。使用更短的反应时间、更低的温度 （∼130 °C） 和二硫醇（例如乙烷-1,2-二硫醇）还可以分离铼-二硫醇酸钙，这是通往 ReS 酸钙的过程中的假定中间体。ReS 腐蚀树脂在其循环伏安图中表现出高热稳定性和两种可逆氧化和还原，其氧化还原电位与观察到的类似 ReO 腐蚀树脂几乎相同。复合物的电化学 HOMO-LUMO 间隙在 2.2 eV 时与以配体为中心的氧化和还原一致。另一方面，ReS 腐蚀剂的紫外-可见光谱与 ReO 对应物的紫外-可见光谱明显不同。标量相对论 DFT 计算表明，这种差异反映了低能 LUMO+2 和 LUMO+3 水平，包括 Re-S π反键相互作用;相比之下，ReO 蛋白表现出更大的 LUMO+1/LUMO+2 间隙，正如相对经典的 Gouterman 型金属卟啉类似物所预期的那样。ReS 腐蚀剂的高稳定性与地球化学家将铼视为中等亲黄铜元素（即分裂成硫化物熔体的元素）的观点以及最近对亲硫性的定量分析一致，该分析表明铼的亲氧性和亲硫性基本上是均匀平衡的。