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Updated: Sep 25, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Synthesis and study of C-substituted methylthio derivatives of cobalt bis(dicarbollide)
Marina Yu Stogniy1, Olga N Kazheva2, Denis M Chudak3
1A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences 28 Vavilov Str. Moscow 119991 Russia sivaev@ineos.ac.ru.
Abstract:
The C-methylthio derivatives of cobalt bis(dicarbollide) were synthesized by reaction of anhydrous CoCl2 with nido-carborane [7-MeS-7,8-C2B9H11]- and isolated as a mixture of rac-[1,1'-(MeS)2-3,3'-Co(1,2-C2B9H10)2]- and meso-[1,2'-(MeS)2-3,3'-Co(1,2-C2B9H10)2]- isomers. The structures of both isomers were studied using DFT quantum chemical calculations. The most preferable geometry of rotamers and the stabilization energy of C-methylthio derivatives of cobalt bis(dicarbolide) were calculated. The (BEDT-TTF)[1,1'-(MeS)2-3,3'-Co(1,2-C2B9H10)2] salt was prepared and its structure was determined by single crystal X-ray diffraction. The cisoid conformation of the rac-[1,1'-(MeS)2-3,3'-Co(1,2-C2B9H10)2]- 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.
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