Abstract

Reactions of electrochemically generated antimony(V) and tin(IV) complex species containing a tridentate O,N,O-donor ligand with various thiols were studied. Among main group metal complexes with N,N-bis(2-hydroxy-di-3,5-tert-butylphenyl)amine (CatH₂–NH–CatH₂), compounds [Me₂Sn(Cat-N-SQ)] (I), [Et₂Sn(Cat-N-SQ)] (II), [Ph₂Sn(Cat-N-SQ)] (III), [(c-C₆H₁₁)₂Sb(Cat-N-Cat)] (IV), and [Ph₃Sb(Cat-NH-Cat)] (V) are the most active, able to mediate the oxidation of thiols (1-hexanethiol, cyclohexanethiol, and 4-methoxythiophenol), to symmetrical disulfides were identified. The anodic activation of Sb(V) and Sn(IV) complexes involves organic ligands and gives rise to intermediates that react with thiols. During the mediated electrosynthesis, the initial complex species is regenerated in solution. The use of metal complex mediators decreases the anodic overvoltage of the thiol oxidation in comparison with direct electrochemical synthesis. The yields of products depend on complex and thiol structures or ratio. The highest efficiency in the electrocatalytic reactions was found for the [Ph₃Sb(Cat-NH-Cat)] complex, which should be used for the synthesis of disulfides.

中文翻译：

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对称二硫化物电合成中锑（V）和锡（IV）与氧化还原活性 O,N,O-供体配体的配合物

摘要

研究了电化学生成的含有三齿 O、N、O 供体配体的锑 (V) 和锡 (IV) 配合物与各种硫醇的反应。在与N , N -双(2-羟基-二-3,5-叔丁基苯基)胺 (CatH ₂ –NH–CatH ₂ ) 的主族金属络合物中，化合物 [Me ₂ Sn(Cat-N-SQ)] ( I ), [Et ₂ Sn(Cat-N-SQ)] ( II ), [Ph ₂ Sn(Cat-N-SQ)] ( III ), [(cC ₆ H ₁₁ ) ₂ Sb(Cat-N- Cat)] ( IV ) 和 [Ph ₃ Sb(Cat-NH-Cat)] ( V) 是最活跃的，能够介导硫醇（1-己硫醇、环己硫醇和 4-甲氧基苯硫酚）氧化成对称的二硫化物。Sb(V) 和 Sn(IV) 配合物的阳极活化涉及有机配体并产生与硫醇反应的中间体。在介导的电合成过程中，最初的复杂物质在溶液中再生。与直接电化学合成相比，金属配合物介体的使用降低了硫醇氧化的阳极过电压。产物的产率取决于复合物和硫醇结构或比例。[Ph ₃ Sb(Cat-NH-Cat)]配合物的电催化反应效率最高，应用于合成二硫化物。