Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. 2. Four Convenient, High-Yield Solid-State Syntheses of the Hexatungsten Dodecachloride Cluster W6Cl12and Cluster Acid (H3O)2[W6(μ3-Cl)8Cl6](OH2)x, Including New Cation-Assisted Ternary Routes
- 1 July 1998
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 37 (15) , 3660-3663
- https://doi.org/10.1021/ic980232n
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.Keywords
This publication has 27 references indexed in Scilit:
- Synthesis, Characterization, and Structure of Mixed Chloride−Selenide Tungsten Cluster ComplexesInorganic Chemistry, 1997
- Resonance Raman Spectra of [M6X8Y6]2-Cluster Complexes (M = Mo, W; X, Y = Cl, Br, I)Inorganic Chemistry, 1996
- High-Yield Synthesis of the W6S8 Cluster Unit as the Pyridine Complex (W6S8)(py)6 and Attempts To Prepare Tungsten Analogs of the Chevrel PhasesInorganic Chemistry, 1995
- Synthesis, structure and electronic properties of octakis(.mu.3-sulfido)hexakis(triethylphosphine)hexatungsten as a tungsten analog of the molecular model for superconducting Chevrel phasesInorganic Chemistry, 1989
- Hexanuclear tungsten cluster structures: tetradecachlorohexatungstate(2-), tetradecabromohexatungstate(2-), and tetradecaiodohexatungstate(2-) relevance to unusual emissive behaviorInorganic Chemistry, 1986
- Spectroscopic, electrochemical, and photochemical properties of molybdenum(II) and tungsten(II) halide clustersJournal of the American Chemical Society, 1983
- Chemistry of the polynuclear metal halides. XII. Preparation of molybdenum and tungsten M6X84+ clusters by reduction of higher halides in molten sodium halide--aluminum halide mixturesInorganic Chemistry, 1974
- Chemistry of polynuclear metal halides. V. Reactions and characterization of compounds containing tungsten halide cluster speciesInorganic Chemistry, 1970
- Über die Chloride des zweiwertigen Molybdän, Wolframs und Tantals. IV Mitteilung. Die Derivate des 3‐ Wolfram‐6‐chloridesZeitschrift für anorganische und allgemeine Chemie, 1924
- Über die Chloride des zweiwertigen Molybdäns, Wolframs und Tantals. (Nach Versuchen von Emma Haller, Herbert Helwig, Antonie Köhler und Hellmut Feit.) (Erste Mitteilung)Berichte der deutschen chemischen Gesellschaft (A and B Series), 1922