Thiolate Chemistry of the Iron Group Elements: Synthesis and Structure of the Complexes [Co2{o‐(SCH2)2C6H4}3]2⊖ and [Ni3{o‐(SCH2)2C6H4}4]2⊖

The novel complex anions 1 and 2 with the ligand “S2-o-xyl” (o-xylene-α,α′-dithiolate) were prepared from CoCl2 and NiCl2, respectively, and S2-o-xyl2⊖. The Co2-complex 1 is an example of the rare syn-exo arrangement of the thiolate S atoms in the central Co2S2 ring. In the Ni3-complex 2, each of the Ni atoms is planar-coordinated by four sulfur atoms; the Ni3-skeleton is bent.