Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12 and Cluster Acid (H3O)2[W6(μ3-Cl)8Cl6](OH2)x, Including New Cation-Assisted Ternary Routes

Vladimir Kolesnichenko; Louis Messerle

doi:10.1021/ic980232n

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Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12 and Cluster Acid (H3O)2[W6(μ3-Cl)8Cl6](OH2)x, Including New Cation-Assisted Ternary Routes

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Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12 and Cluster Acid (H3O)2[W6(μ3-Cl)8Cl6](OH2)x, Including New Cation-Assisted Ternary Routes

Vladimir Kolesnichenko and Louis Messerle

Inorganic chemistry, Vol.37(15), pp.3660-3663

07/01/1998

DOI: 10.1021/ic980232n

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Abstract

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(μ3-Cl)8Cl6](OH2)x, recrystallization, and thermolysis in vacuo. Antimony was a less effective reductant because of the lower yield of chloro acid (31%) and the substantial quantities of insoluble byproducts found after HCl workup. The yield of (H3O)2[W6(μ3-Cl)8Cl6](OH2)x from WCl6 reduction by Sb improved dramatically to 79% with added KCl, while LiCl reduced the yield to only traces. In Bi reduction of WCl6, the yield of (H3O)2[W6(μ3-Cl)8Cl6](OH2)x decreased from 86 to 49% upon addition of NaCl, whereas added KCl had no effect on the yield. The Hg-, Bi-, Sb/KCl-, and Bi/KCl-based routes offer substantial experimental advantages over published methods for preparation of (H3O)2[W6(μ3-Cl)8Cl6](OH2)x and W6Cl12.

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Title: Subtitle: Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12 and Cluster Acid (H3O)2[W6(μ3-Cl)8Cl6](OH2)x, Including New Cation-Assisted Ternary Routes
Creators: Vladimir Kolesnichenko - Department of Chemistry, The University of Iowa, Iowa City, Iowa 52242
Louis Messerle - Department of Chemistry, The University of Iowa, Iowa City, Iowa 52242
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.37(15), pp.3660-3663
DOI: 10.1021/ic980232n
ISSN: 0020-1669
eISSN: 1520-510X
Language: English
Date published: 07/01/1998
Academic Unit: Chemistry; Radiology
Record Identifier: 9984216586502771

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