New ligands incorporating carboranyl units in organic fragments NS2 (pyridine-dithia) or S′S2 (thiophene-dithia) have been synthesized. The closo species of these ligands were obtained by the reaction of sodium thiolate-o-carborane with the corresponding difunctional electrophile derivatives of pyridine or thiophene. Partial degradation of the closo species derivatives of pyridine was successfully achieved with KOH in ethanol at r.t. All these compounds have been characterized by chemical analyses and NMR techniques. The 1H-NMR spectrum of the nido species shows that these nido molecules are produced in stoichiometric purity but not in isomeric purity. The crystal structure of 2,6-bis(((1-methyl-1,2-dicarba-closo-dodecabo-ranyl)thio)methyl)pyridine is reported and confirms that the carborane cages are closo and connected to both sulfur atoms. These, through methylene bridges, are connected to the pyridine at the 2 and 6 positions.