Tungsten hexachloride was reduced by Hg or Bi at moderately low temperatures (~350
C) to afford good yields(Hg, 73%; Bi, 85%) of W
6Cl
12 after conversion of the reduction product to the chloro acid (H
3O)
2[W
6(
3-Cl)
8Cl
6](OH
2)
x, recrystallization, and thermolysis in vacuo. Antimony was a less effective reductant because of thelower yield of chloro acid (31%) and the substantial quantities of insoluble byproducts found after HCl workup.The yield of (H
3O)
2[W
6(
3-Cl)
8Cl
6](OH
2)
x from WCl
6 reduction by Sb improved dramatically to 79% with addedKCl, while LiCl reduced the yield to only traces. In Bi reduction of WCl
6, the yield of (H
3O)
2[W
6(
3-Cl)
8Cl
6](OH
2)
x decreased from 86 to 49% upon addition of NaCl, whereas added KCl had no effect on the yield. TheHg-, Bi-, Sb/KCl-, and Bi/KCl-based routes offer substantial experimental advantages over published methodsfor preparation of (H
3O)
2[W
6(
3-Cl)
8Cl
6](OH
2)
x and W
6Cl
12.