Mononuclear benzenethiolato nickel and palladium complexes are prepared by reactions of orgaonickel and -palladium complexes with sulfur-containing compounds such as benzenethiol, phenyl sulfide, and diphenyl disulfide. Thermolysis of phenyl(benzenethiolato)nickel complex with PEt₃ causes reductive elimination of phenyl sulfide, while a methyl(benzenethiolato)nickel complex does not undergo thermally induced reductive elimination of methyl(phenyl)sulfide. Reaction of phenyl benzenecarbothioate with Ni(cod)₂ in the presence of PEt₃ above 60 °C gives phenyl sulfide through initial oxidative addition of the substrate to give benzoyl(benzenethiolato)nickel intermediate that undergoes ensuing reductive elimination of the product. Palladium(0) complexes catalyze decarbonylation of thiol ester to the corresponding sulphide. Rh(I) complex promoted decarbonylation of thiol esters of substituted acrylic acids gives phenyl alkenyl sulfides which are synthetic equivalents of the carbonyl compounds. Thermal degradation of bis(benzenethiolato)nickel complexes causes elimination of diphenyl sulfide accompanied by formation of nickel sulfide. Thermolysis of hydrido(benzenethiolato)- and methyl(benzenethiolato)nickel complexes as well as their palladium analog also gives organic products some of which are derived from C-S bond cleavage of the thiolato ligand. This observation is applied to preparation of zinc and cadmium sulfide using thermolysis of methanethiolato complexes of these metals.