Treatment of ortho-carborane, n-butyl lithium, sulfur, and CpCo(CO)I-2 with differing ratios led to four new compounds [(CpCoS2C2B10H10)(CpCoSC2B10F11)(SC4H9)] (3), [(CpCO)(2)S-2(S2C2B10H10)(SC2B10H10)(SC4F19)] (4), [(CpCo)(2)-Co(SC4H9)(6)](+)[Co(S2C2B10H10)(2)](-) (5), and [(CpCo)(2)Co(SC2B10H11)(SC4H9)(5)](+)[Co(S2C2B10H10)(2)](-) (6). Compound 3 contains a rhombic Co-2(mu(2)-S)(2) core and can be considered as an adduct of the two 16e half-sandwich monomers CpCo(S2C2B10H10) (1) and CpCo(SC4H9)(SC2B10H11). Compound 4 is a trinuclear complex containing a cuboidal [Co-3(mu(3)-S)(2)(mu-S)(2)] core, and one cobalt atom is coordinated by six sulfur atoms in a distorted octahedral geometry. Compound 5 consists of a linear-type trinuclear cobalt(III) monocation bridged by six n-butyl thiolato units and a square-planar cobalt(III) monoanion [Co(S2C2B10H10)(2)](-). However, in 6, one ortho-carborane monothiolato ligand [SC2B10H11](-) has replaced one n-butyl thiolato ligand in 5. This leads to a nonlinear arrangement of the three cobalt atoms in the cation and the nonplanar [Co(S2C2B10H10)(2)](-) anion in 6. Interestingly, the treatment of the 16e half-sandwich CpCo(S2C2B10H10) (1) by [N(n-Bu)(4)]Br afforded the ionic compound 7, [N(n-Bu)(4)](+)[Co(S2C2B10H10)(2)](-), containing a square-planar anion.