Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12
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- 作者：Vladimir Kolesnichenko and Louis Messerle
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：July 27, 1998
- 年：1998
- 卷：37
- 期：15
- 页码：3660 - 3663
- 全文大小：47K
- 年卷期：v.37,no.15(July 27, 1998)
- ISSN：1520-510X
文摘
Tungsten hexachloride was reduced by Hg or Bi at moderately low temperatures (~350 
C) to afford good yields(Hg, 73%; Bi, 85%) of W6Cl12 after conversion of the reduction product to the chloro acid (H3O)2[W6(
3-Cl)8Cl6](OH2)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 (H3O)2[W6(3-Cl)8Cl6](OH2)x from WCl6 reduction by Sb improved dramatically to 79% with addedKCl, while LiCl reduced the yield to only traces. In Bi reduction of WCl6, the yield of (H3O)2[W6(3-Cl)8Cl6](OH2)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 (H3O)2[W6(3-Cl)8Cl6](OH2)x and W6Cl12.
C) to afford good yields(Hg, 73%; Bi, 85%) of W6Cl12 after conversion of the reduction product to the chloro acid (H3O)2[W6(3-Cl)8Cl6](OH2)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 (H3O)2[W6(3-Cl)8Cl6](OH2)x from WCl6 reduction by Sb improved dramatically to 79% with addedKCl, while LiCl reduced the yield to only traces. In Bi reduction of WCl6, the yield of (H3O)2[W6(3-Cl)8Cl6](OH2)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 (H3O)2[W6(3-Cl)8Cl6](OH2)x and W6Cl12.