New Tungsten Chloride Cluster Compounds Containing Iron or Cobalt: MW₂Cl₁₀ and MW₆Cl₁₄ (M = Fe, Co)

Abstract

The reduction of tungsten hexachloride with iron powder or cobalt powder resulted in the formation of MW2Cl10 (M = Fe and Co) in fused silica tubes at 250 °C and 225 °C, respectively. Crystal structures of the new compounds were refined isotypically from X‐ray powder diffraction patterns [C2/c, Z = 4, a = 6.1226(1) Å, b = 16.7943(1) Å, c = 12.3737(1) Å, and β = 108.99(1)° for FeW2Cl10, and a = 6.111(1) Å, b = 16.696(1) Å, c = 12.384(1) Å, and β = 108.97(1)° for CoW2Cl10]. The structures of Fe1/5W2/5Cl2 and Co1/5W2/5Cl2 can be considered as a cation‐deficient CdI2‐type structure, in which bioctahedral [W2Cl10]n– anions with n ≈︁ 2 introduce significant distortions. The compounds MW6Cl14 (M = Fe and Co) were prepared following the same procedure at 475 °C. Their crystal structures were refined isotypically [Pn3, Z = 4, a = 12.567(1) Å for FeW6Cl14, and 12.525(1) Å for CoW6Cl14] to the structure of PbMo6Cl14 from X‐ray powder diffraction patterns.

Alkaline Earth Cluster Compounds AE[W6I14] and the Solvate [Ca(C2H6SO)6][W6I14]

“…The crystal structure of AE [W 6 I 14 ] can be viewed as a hierarchical rock‐salt structure in which ( AE ) 2+ and [W 6 X 14 ] 2– units substitute for Na + and Cl – in the structure of NaCl. Corresponding structures are reported for T [ M 6 X 14 ] compounds with divalent cations T = Pb, Hg, Fe, Co, Cd (with M = Mo, W, and X = Cl, Br, I) …”

From WCl6 to WCl2: Properties of Intermediate Fe–W–Cl Phases

“…More octahedral sites are occupied with iron ions, indicated with numbers for FeW 2 Cl 10 (1) and Fe 2 W 2 Cl10 (1 and 2). For (Fe,W) 1−x Cl 2 (or Fe 1−x W 2/3x Cl 2 ) we assume a variable (phase-width) cation distribution pattern over all kinds of octahedral sites.…”

Low-temperature preparation of tungsten halide clusters: Crystal structure of the adduct W5Br12 · SbBr3

“…Such a sequence of products was also obtained when reducing WCl 6 with iron or cobalt metal (M). Only the structures of two compounds (MW 2 Cl 10 and MW 6 Cl 14 ) are fully characterized so far, out of several ones being obtained [13].…”