The metal-metal-bonded cations [Ag2Pt3(R2dtc)6]2+, consisting of Pt(R2dtc)2 units acting as ligands toward Ag(I), are observed in electrospray mass spectra as intact ions and also as the monoanion adducts [Ag2Pt3(R2dtc)6X]+ (X- = ClO4-, NO3-). When solutions containing two different Pt(R2dtc)2 complexes and Ag(I) are mixed, there is global scrambling of dithiocarbamate ligands on platinum in the Ag/Pt/R2dtc cations within 1 h, which is much faster than exchange in the absence of Ag(I). Hg(R2dtc)2 complexes also act as ligands toward Ag(I), and the cations [AgHg2(R2dtc)4]+ are readily observed. Mixtures of two different Hg(R2dtc)2 complexes with Ag(I) give the expected global scrambling of the dithiocarbamates on mercury. Interaction between M(R2dtc)3 (M = Co, Rh, Ir) and Ag(I) leads to the observation of [AgM2(R2dtc)6]+ cations, and mixing of different M(R2dtc)3 compounds with Ag(I) leads to exchange of complete M(R2dtc)3 units on Ag but not global dithiocarbamate ligand exchange on cobalt. However, fast global exchange of dithiocarbamate ligands on cobalt and mercury, as well as interchange of metals to give trimetallic species containing Ag, Co, and Hg, is observed when mixtures of Co(R2dtc)3, Hg(R’2dtc)2, and Ag(I) are examined by ESMS. Similar global ligand exchange does not occur when Rh(R2dtc)3 or Ir(R2dtc)3 is mixed with Hg(R’2dtC)2 and Ag(I), although exchange of complete metal dithiocarbamate units on Ag(I) does still occur to give mixed Ag/Rh/Hg cations. Sulfur insertion occurs with the iridium complexes to give [AgIr2(R2dtc)5(R2dtcS)]+ and AgIr2(R2dtc)4(R2dtcS)2]+. These results indicate that an extensive new chemistry of neutral metal dithiocarbamates exists in which they behave as ligands toward metal cations. Reaction of silver salts with the dithiocarbamates of Zn(II) and Pb(II) leads to formation of non-silver-containing metal-rich dithiocarbamate cations of the types [M2(R2dtc)3]+ and [M2(R2dtc)5]+(M=Zn,Pb). Silver(I) salts simply oxidize the dithiocarbamates of Fe(III) and Ni(II) to give the known [Fe(R2dtc)3]+ and [Ni(R2dtc)3]+ species.