[en] Complexation of M(CO)₃⁺ (M = Tc, Re) with dithiocarbamato-carboxylate ligands was studied. It was found that the dithiocarbamate chelation unit has rather high affinity to M(CO)₃⁺ species and the resulting complexes are extremely stable in a wide pH range. The complex M(CO)₃[S₂CN(CH₂COO)₂] is monomeric in solution (ESI MS) and dimeric in the crystal phase (single-crystal XRD). The 'scorpion-like' dithiocarbamato-carboxylate ligands were prepared; it was shown that C₅ chain is long enough to reach back to the free coordination vacancy in M(CO)₃⁺ core and to block it. (author)