Abstract

Heating WTe(2), Te, and Br(2) at 390 degrees C followed by extraction with KCN gives [W(3)Te(7)(CN)(6)](2-). Crystal structures of double salts Cs(3.5)K{[W(3)Te(7)(CN)(6)]Br}Br(1.5).4.5H(2)O (1), Cs(2)K(4){[W(3)Te(7)(CN)(6)](2)Cl}Cl.5H(2)O (2), and (Ph(4)P)(3){[W(3)Te(7)(CN)(6)]Br}.H(2)O (3) reveal short Te(2)...X (X = Cl, Br) contacts. Reaction of polymeric Mo(3)Se(7)Br(4) with KNCSe melt gives [Mo(3)Se(7)(CN)(6)](2-). Reactions of polymeric Mo(3)S(7)Br(4) and Mo(3)Te(7)I(4) with KNCSe melt (200-220 degrees C) all give as final product [Mo(3)Se(7)(CN)(6)](2)(-) via intermediate formation of [Mo(3)S(4)Se(3)(CN)(6)](2-)/[Mo(3)SSe(6)(CN)(6)](2-) and of [Mo(3)Te(4)Se(3)(CN)(6)](2-), respectively, as was shown by ESI-MS. (NH(4))(1.5)K(3){[Mo(3)Se(7)(CN)(6)]I}I(1.5).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 W(3)Te(7)Br(4) 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.6H(2)O (5) and K(5)[W(3)(mu(3)-Te)(mu-Se)(3)(CN)(9)] (6) were isolated. X-ray analysis of 5 reveals the presence of a new TeSe(2-) ligand. The complexes were characterized by IR, Raman, electronic, and (77)Se and (125)Te NMR spectra and by ESI mass spectrometry.

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