Abstract

A series of triarylantimony(V) complexes with p-dimethylaminopyridine and р-cyanopyridine of the general formulas [(Cat)SbAr₃(р-Me₂N–Py)] (complexes I–IV) and [(Cat)SbAr₃(р-CN–Py)] (complexes V–VII) has been synthesized. Their molecular structures and electrochemical properties have been studied. 3,6-Di-tert-butyl-o-benzoquinone, 4,5-piperazine-1,4-diyl-3,6-di-tert-butyl-o-benzoquinone, and 4,5-dichloro-3,6-di-tert-butyl-o-benzoquinone are used as redox-active ligands. The molecular structures of several complexes in the crystalline state are determined by X-ray diffraction analysis (CIF files CCDC nos. 1974173 (I ⋅ 0.5toluene), 1974174 (II ⋅ 2toluene), 1974175 (V), 1974176 (VI ⋅ hexane), and 1974177 (VII)). All complexes have a distorted octahedral structure, and an additional neutral pyridine ligand occupies one of the apical positions. Electrochemical transformations of the complexes are studied by cyclic voltammetry in a dichloromethane solution. The introduction of substituted pyridine into the molecule of the complex does not change the electrooxidation mechanism of the complexes. For all complexes with р-dimethylaminopyridine, both oxidation potentials are shifted to the cathodic region (0.13–0.21 V for the potential of the first oxidation process and to 0.3–0.4 V for the potential of the second oxidation process). A similar shift for the complex with p-cyanopyridine is less pronounced (0.05 V for the potential of the first oxidation process of complex V as compared to that of complex I).

中文翻译：

---

单核锑（V）邻苯二甲酸酯配合物与其他吡啶配体

摘要

一系列triarylantimony（V）络合物与p二甲基氨基吡啶和р通式氰基吡啶[（CAT）SBAR ₃（р -Me ₂的N- PY）]（络合物我- IV）和[（CAT）SBAR ₃（р -CN–Py）]（络合物V – VII）已合成。已经研究了它们的分子结构和电化学性质。3,6-二-叔丁基- ø苯醌，4,5-哌嗪-1,4-二基-3,6-二-叔丁基- Ò苯醌和4,5-二氯-3,6-二-叔丁基邻苯醌用作氧化还原活性配体。（CIF文件CCDC号1974173（几个复合物在结晶状态的分子结构通过X射线衍射分析来确定余⋅0.5toluene），1974174（II ⋅2toluene），1974175（V），1974176（VI ⋅己烷） ，以及1974177（VII））。所有复合物均具有扭曲的八面体结构，并且另外的中性吡啶配体占据顶部位置之一。通过在二氯甲烷溶液中的循环伏安法研究配合物的电化学转化。将取代的吡啶引入复合物的分子中不会改变复合物的电氧化机理。对于所有配合物р-二甲基氨基吡啶，两个氧化电位都移至阴极区域（第一个氧化过程的电位为0.13-0.21 V，第二个氧化过程的电位为0.3-0.4 V）。具有对-氰基吡啶的配合物的类似变化不太明显（与配合物I相比，配合物V的第一氧化过程的电势为0.05V ）。