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The mononuclear complex (BzMe3N)2[V(mp)3] · MeCN · 1/2 MeOH (1) (mp = o-SC6H4O2−) obtained by reacting VCl3 with Na2mp in the presence of BzMe3NBr contains the synthon [V(mp)3]2−. Further reaction with Co2(CO)8 gave [V(mp)3Co(Py)2(MeCN)] · 2MeCN (2) and [V(mp)3Co(DMF)3] (3), depending on the recrystallization conditions. The coordination geometry of the V atoms in all these complexes lies between an octahedron and a trigonal prism. Upon formation of (2) and (3), the terminal oxo atoms of mp become μ2-O bridges between V and Co, while the latter atom is also octahedral.