The dimeric W-V complex [Et4N](4)[syn-{O=W(NCS)(3)}(2)(mu-S)(2)], 1, prepared from [Et4N](2)[WS4], SCN-, and Cd2+, shows interesting reactivity patterns in that the thiocyanate trans to the oxc, group can in part be replaced, initiated by Mn2+, by dimethylformamide (DMF) to form [Et4N](2.5)[{O=W(NCS)(2.25)(DMF)(1.25)}(2)(mu-S)(2)], 2. With Ag+, 1 undergoes partial replacement of SCN- by DMF and coordinates to the silver ions to generate {[Et4N](2.5)[{W2O2(NCS)(2)(mu-S)(2)}(mu-NCS)(2)(DMF){Ag-0.5(SCN)}]}(n), 3. Compound 3 constitutes a polymeric double-stranded chain, with normal bonding interactions [via W-(mu-NCS)-Ag] between the two strands, and moderate intrastrand [W-(mu-NCS)Ag-...] bonding. The crystal and molecular structures of the three compounds are described.