The dimeric W
V complex [Et
4N]
4[
syn-{O=W(NCS)
3}
2(
-S)
2],
1, prepared from [Et
4N]
2[WS
4], SCN
-, and Cd
2+, showsinteresting reactivity patterns in that the thiocyanate
trans to the oxo group can in part be replaced, initiated byMn
2+, by dimethylformamide (DMF) to form [Et
4N]
2.5[{O=W(NCS)
2.25(DMF)
1.25}
2(
-S)
2],
2. With Ag
+,
1 undergoespartial replacement of SCN
- by DMF and coordinates to the silver ions to generate {[Et
4N]
2.5[{W
2O
2(NCS)
2(
-S)
2}(
-NCS)
2(DMF){Ag
0.5(SCN)}]}
n,
3. Compound
3 constitutes a polymeric double-stranded
chain, with normalbonding interactions [via W-(
-NCS)-Ag] between the two strands, and moderate intrastrand [W-(
-NCS)···Ag]bonding. The crystal and molecular structures of the three compounds are described.