The reaction of (Me3SiNSN)(2)S with TeCl4 in CH2Cl2 affords Cl2TeS2N2 (1) and that of (Me3SiNSN)(2)Se with TeCl4 produces Cl2TeSeSN2 (2) in good yields. The products were characterized by X-ray crystallography, as well as by NMR and vibrational spectroscopy and El mass spectrometry. The Raman spectra were assigned by utilizing DFT molecular orbital calculations. The pathway of the formation of five-membered Cl2TeESN2 rings by the reactions of (Me3SiNSN)(2)E with TeCl4 (E S, Se) is discussed. The reaction of (Me3SiNSN)(2)Se with [PPh4]2[Pd2X6] yields [PPh4](2)[Pd-2(mu-Se2N2S)X-4] (X Cl, 4a; Br, 4b), the first examples of complexes of the (Se2N2S)(2-) ligand. In both cases, this ligand bridges the two palladium centers through the selenium atoms.