A TG, DTG, and DSC study of Ni[S2CN(C3H5)(2)](2).H2O and Cu[S2CN(C3H5)(2)](2) has been reported together with the associated thermal decomposition mechanisms. These mechanisms are rationalized in terms of the structure of the complexes and the nature of the intermediate products and final residues. The thermal analysis to NiS occurs by initial elimination Of S2CN(C3H5)(2), C3H5 and subsequent loss of C3H5-N=C=S. While the pyrolysis to CuS occurs via Cu[S2CN(C3H5)(2)][SCN-C3H5] and by sequential elimination of S2CN(C3H5)(2) followed by elimination of RCN. These dithiocarbamate complexes, thus provide a source for metal sulfide materials such as NiS and CuS. (C) 2004 Elsevier B.V. All rights reserved.