Stogniy Marina Yu, Kazheva Olga N, Chudak Denis M, Shilov Gennady V, Filippov Oleg A, Sivaev Igor B, Kravchenko Andrey V, Starodub Vladimir A, Buravov Lev I, Bregadze Vladimir I, Dyachenko Oleg A
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences 28 Vavilov Str. Moscow 119991 Russia
Institute of Problems of Chemical Physics, Russian Academy of Sciences 1 Semenov Av., Chernogolovka Moscow Region 142432 Russia.
RSC Adv. 2020 Jan 16;10(5):2887-2896. doi: 10.1039/c9ra08551c. eCollection 2020 Jan 14.
The -methylthio derivatives of cobalt bis(dicarbollide) were synthesized by reaction of anhydrous CoCl with -carborane [7-MeS-7,8-CBH] and isolated as a mixture of -[1,1'-(MeS)-3,3'-Co(1,2-CBH)] and -[1,2'-(MeS)-3,3'-Co(1,2-CBH)] isomers. The structures of both isomers were studied using DFT quantum chemical calculations. The most preferable geometry of rotamers and the stabilization energy of -methylthio derivatives of cobalt bis(dicarbolide) were calculated. The (BEDT-TTF)[1,1'-(MeS)-3,3'-Co(1,2-CBH)] salt was prepared and its structure was determined by single crystal X-ray diffraction. The cisoid conformation of the -[1,1'-(MeS)-3,3'-Co(1,2-CBH)] anion is stabilized by short intramolecular CH⋯S hydrogen and BH⋯S chalcogen bonds between the dicarbollide ligands, that is in good agreement with the data of quantum chemical calculations.
通过无水氯化钴与7-甲硫基-7,8-碳硼烷[7-MeS-7,8-C₂B₉H₁₁]反应合成了钴双（二碳硼烷）的甲硫基衍生物，并分离得到了α-[1,1'-（甲硫基）-3,3'-Co(1,2-C₂B₉H₁₁)]和β-[1,2'-（甲硫基）-3,3'-Co(1,2-C₂B₉H₁₁)]异构体的混合物。使用密度泛函理论（DFT）量子化学计算研究了两种异构体的结构。计算了钴双（二碳硼烷）甲硫基衍生物的旋转异构体的最优选几何结构和稳定能。制备了（BEDT-TTF）[1,1'-（甲硫基）-3,3'-Co(1,2-C₂B₉H₁₁)]盐，并通过单晶X射线衍射确定了其结构。α-[1,1'-（甲硫基）-3,3'-Co(1,2-C₂B₉H₁₁)]阴离子的顺式构象通过二碳硼烷配体之间短的分子内CH⋯S氢键和BH⋯S硫属元素键得以稳定，这与量子化学计算数据吻合良好。
