Bis(μ‐N,N‐dimethyldithiocarbamato‐κ3S,S′:S′)bis[(dimethoxyphenylphosphane‐κP)(N,N‐dimethyldithiocarbamato‐κ2S,S′)cobalt(III)] bis(hexafluorophosphate)

Purple prismatic crystals of the title compound, Co₂(C₃H₆NS₂)₄(C₈H₁₁O₂P)₂](PF₆)₂, were obtained by repeated recrystallization of trans‐Co(C₃H₆NS₂)₂‐(C₈H₁₁O₂P)₂]PF₆ from CH₃CN/Et₂O and then from MeOH/CH₂Cl₂; during recrystallization one of the P(OMe)₂Ph ligands was dissociated from the Co^III center and the resulting Co^III complex fragment underwent dimerization. The complex cation has a dinuclear structure bridged by one S atom of each of two of the N,N‐di­methyl­di­thio­carbamate ligands, and has crystallographically imposed C₂ symmetry. Two P(OMe)₂Ph ligands are coordinated at the transoid positions of the Co₂(μ‐C₃H₆NS₂)₂(C₃H₆NS₂)₂ moiety, with Co—P bond lengths of 2.1921 (11) Å.