Charge-compensated nido -carboranyl thioether ligands [7-MeS-10-Me ₂ S-7,8-C ₂ B ₉ H ₁₀ ] and [7,8-(MeS) ₂ -10-Me ₂ S-7,8-C ₂ B ₉ H ₉ ] and tungsten carbonyl complexes on their base were prepared.

Reaction of ortho-carborane with anhydrous AlCl₃ in chloroform results in a mixture of 9-chloro, 9,12-dichloro, and 8,9,12-trichloro derivatives with 9,12-dichloro-ortho-carborane being the main product. Molecular crystal structure of 9,12-dichloro-ortho-carborane was determined by the single crystal X-ray diffraction. The crystal structure of 9,12-Cl₂-1,2-C₂B₁₀H₁₀ appeared to be nearly isostructural to 9,12-dibromo-ortho-carborane: the crystal packing is built of layers in which molecules are connected via weak hydrogen and halogen bonds. A synthetic scheme for preparation of the hexachloro derivative of cobalt bis(dicarbollide) Cs[8,8′,9,9′,12,12′-Cl₆-3,3′-Co(1,2-C₂B₉H₈)₂] from 9,12-dichloro-ortho-carborane has been proposed.

Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)₂-3,3′-M(1,2-C₂B₉H₁₀)₂]⁻ (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph₃P)ClPd[8,8′- (MeS)₂-3,3′-Co(1,2-C₂B₉H₁₀)₂-κ²-S,S′]} and {(COD)Rh[8,8′-(MeS)₂-3,3′-Co(1,2-C₂B₉H₁₀)₂-κ²-S,S′]} were determined by single crystal X-ray diffraction.