Monometallic [Pt{S-S2C2(NR)(2)H}(2)] (S-S2C2(NR)(2)H = kappa(2)-S,S-S2C2(NR)(2)H = bis-dialkyl-dithioxamidate, R = methyl, isoamyl, benzyl) and binuclear and trinuclear heterobimetallic complexes [Pt{S-S2C2(NR)(2)H}{mu-S2C2(NR)(2)}MLn] (mu-S2C2(NR)(2) = kappa(2)-S,S(Pt)-kappa(2)-N,N(M)-S2C2(NR)(2)) and [Pt{{mu-S2C2(NR)(2)}MLn}(2)] (MLn+ = [(eta(3)-allyl)palladium](+), [bis(2-phenylpyridine)rhodium](+), [(eta(6)-p-cymene)(chloro) ruthenium](+), [(1,4-cyclooctadiene)rhodium](+), [(pentamethylcyclopentadienyl)(chloro)rhodium](+)) have been prepared and characterized. The progressive substitution of the residual amidic hydrogen in the [Pt{S-S2C2(NR)(2)H}(2)] complexes with a MLn+ metal fragment results in the deshielding of platinum nuclei, a red shift of the MLCT absorption maximum, and a decrease in the oxidation potential, Such behavior has been interpreted as a progressive electron shift from platinum to the binucleating ligands, the extent of which depends on the nature of MLn+ metal fragment.