Heating WTe2, Te, and Br-2 at 390 degrees C followed by extraction with KCN gives [W3Te7(CN)(6)](2-). Crystal structures of double salts Cs3.5K{[W3Te7(CN)(6)]Br}Br(1.5)center dot 4.5H(2)O (1), Cs2K4{W3Te7(CN)(6)](2)Cl}Cl center dot 5H(2)O (2), and (Ph4P)(3){[W3Te7(CN)(6)]Br}-H2O (3) reveal short (Te2X)-X-... (X = Cl, Br) contacts. Reaction of polymeric Mo3Se7Br4 with KNCSe melt gives [Mo3Se7(CN)(6)](2-). Reactions of polymeric Mo3S7Br4 and Mo3Te7I4 with KNCSe melt (200-220 degrees C) all give as final product [Mo3Se7(CN)(6)](2-) via intermediate formation Of [Mo3S4Se3(CN)(6)](2-)/[Mo3SSe6(CN)(6)](2-) and of [Mo3Te4Se3(CN)(6)](2-), respectively, as was shown by ESI-MS. (NH4)(1.5)K-3{[Mo3Se7(CN)6]I}I(1.5)center dot 4.5H(2)O (4) was isolated and structurally characterized. Reactions of W(3)Q(7)Br(4) (Q = S, Se) with KNCSe lead to [W(3)Q(4)(CN)(9)](5-). Heating W3Te7Br4 in KCNSe melt gives a complicated mixture Of W(3)Q(7) and W(3)Q(4) derivatives, as was shown by ESI-MS, from which E-3[W-3(mu(3)-Te)(mu-TeSe)(3)(CN)(6)]Br center dot 6H(2)O (5) and K-5[W-3(mu(3)-Te)(mu-Se)(3)(CN)(g)] (6) were isolated. X-ray analysis of 5 reveals the presence of a new TeSe2- ligand. The complexes were characterized by IR, Raman, electronic, and Se-77 and Te-125 NMR spectra and by ESI mass spectrometry.