Copper(I) and silver(I) complexes of dithiomalonamide, N,N'-dimethyl- and N,N'-diphenyldithiomalonamide.

Some copper (I) and silver (I) complexes with dithiomalonamide (Hdtma), NN′-dimethyl-(HMe2dtma) and NN′-diphenyl-dithiomalonamide (HPh2dtma) were prepared: Cu(Hdtma)X (X2 = Cl, Br, I(H2O), ClO4); Cu(HL)2X (HMe2dtma: X = Cl, Br, I, ClO4; HPh2dtma: X = Cl, Br, I); Ag(HL)X (Hdtma: X = Cl; HMe2dtma: X = Br, ClO4, BF4; HPh2dtma: X = Br, I); Ag2(HL)3X2 (Hdtma: X = ClO4, BF4; HMe2dtma: X = Cl; HPh2-dtma: X = Cl, ClO4); Ag2(HMe2dtma)I2 and Ag3(Hdtma)2Br3. Molar conductivities in DMF show that the complexes behave: M2(HL)3(ClO4)2 as 1:2 electrolytes, M(HL) (ClO4 of BF4) as 1:1 electrolytes; those of the halides Cu(HL)X and Cu(HL)2X, are almost equal and intermediate between values for non-electrolytes and 1:1 electrolites. Infrared spectra indicate an S,N-coordination for all the complexes: ν(MN) bands in the region of 400–500 cm−1 and ν(MS) bands in the region of 300–400 cm−1 (for Hdtma), 300–320 cm−1 (for HMe2dtma) and 260–280 cm−1 (for HPh2dtma) are observed. No ν(MX) bands were identified in the halide complexes indicating that a mental—halide coordination, if present in the solid complexes, should be very weak.