Reactions of diphenyllead(IV) chloride with benzil bis(thiosemicarbazone) ((LH6)-H-1) and benzil bis(4-methyl-3-thiosemicarbazone) ((LMe2H4)-Me-1) afforded the first complexes containing the diphenyllead(IV) moiety with bis(thiosemicarbazone) ligands. The new complexes show diverse structural characteristics depending on the ligand and the working conditions. Complexes [PbPh2Cl((LH5)-H-1)]center dot 3H(2)O (1) and [PbPh2Cl((LMe2H3)-Me-1)] (3) are mononuclear species in which the ligands are partially deprotonated and the lead atom has a C2N2S2Cl environment in a distorted pentagonal bipyramid coordination geometry. Complex [PbPh((LMe2H2)-Me-1)](2)center dot 2H(2)O (4) was also obtained, which contains two lead atoms in a binuclear structure with a C2N2S3 coordination sphere for each lead atom, since both dideprotonated ligands act as N2S2 chelate and as sulfur bridge. Reaction from (LH6)-H-1, in the same conditions in which complex 4 was prepared, gave a mixture of products: the lead (II) complex [Pb((LH4)-H-1)](2) (2) and [PbPh3Cl](n). Reactions with the cyclic molecules 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]-triazine-3-thione ((LH2OCH3)-H-2) and 5-methoxy-4-methyl-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]-triazine-3-thione ((LMeHOCH3)-Me-2) were also explored. In all the complexes, the ligands are deprotonated. The complexes [PbPh2(L-2)(2)] (5) and [PbPh2((LMeOCH3)-Me-2)(2)] (7) present the same characteristics. The X-ray structure of 5 shows a distorted octahedral geometry around the lead atom, with the ligand molecules acting as NS chelates, but the nitrogen bonded to the metal is different; one of the triazines shows a novel behavior, since the nitrogen atom of the new imine group formed is the one that is bonded to the lead center, being a good example of linkage isomerism. The complex [PbPh2Cl(L-2)] (6), which was also isolated, could not be crystallized. All the complexes were characterized by elemental analysis, mass spectrometry, IR and H-1, C-13, and Pb-207 NMR spectroscopy and some of them by X-ray diffraction studies.