Three new bis(aryl)triazene ligands, Ar-NNNH-Ar' [Ar = o-C6H4-CO2Me, Ar' = p-C6H4-CH3 (2); Ar = Ar' = o-C6H4-CO2Me (3); Ar = o-C6H4-SMe, Ar' = p-C6H4-CH3) (4)], have been synthesized. The reaction of 1-4 with PdCl2(NCCH3)(2) in the presence of a base afforded a series of binuclear diamagnetic palladium complexes. In these reactions, ligands 1-3 afforded the palladium(I) complexes [Pd-I(o-MeO2C-C6H4-NNN-o-C6H4-CO2Me)](2) (5, monoclinic, space group P2(1)/c, a = 8.6070(10) angstrom, b = 14.3220(10) angstrom, c = 12.7310(10) angstrom, beta = 100.2950(10)degrees, Z = 2), [Pd-I(o-MeO-C6H4-NNN-o-C6H4-OMe)](2) (6, triclinic, space group P1, a = 6.6288(5) angstrom, b = 10.2631(10) angstrom, c = 11.0246(11) angstrom, alpha = 85.579(6)degrees, beta = 80.885(6)degrees, gamma = 74.607(6)degrees, Z = 1), and [Pd-I(o-MeO2C-C6H4-NNN-p-C6H4-CH3)](2) (7, tetragonal, space group I41/a, a = 20.866(3) angstrom, b = 20.866(3) angstrom, c = 13.156(2) angstrom, Z = 8). In contrast, the reaction of ligand 4 with PdCl2(NCCH3)(2) resulted in the formation of a palladium(II) dimer, [Pd-II(o-MeS-C6H4-NNN-p-C6H4-CH3)Cl](2) (8, orthorhombic, space group P2(1)2(1)2, a = 10.4058(5) angstrom, b = 16.2488(8) angstrom, c = 9.9500(5) angstrom, Z = 2).