Chromium hexacarbonyl reacts with (Et2NCS2)2Y (Y Se, Te) in the presence of Me3NO·2H2O to form Cr(S2CNEt2)3. Tungsten hexacarbonyl, under the same conditions, gives rise to WSe2(S2CNEt2)3·0.5H2O (1) and [W(S2CNEt2)4]2W6O19 (2). The structures of 1 and 2 were established by X-ray structural analysis. The tungsten in complex 1 has a distorted dodecahedron coordination. The structure of 2 is ionic, and contains the well known W6O192− anion and the W(S2CNEt2)4+ cation containing dodecahedral tungsten.