Pandora's box of binary tungsten iodides

Abstract

More than 20 binary tungsten iodides have been discovered. This was possible due to a new synthesis of W3I12 through halide exchange reaction and by thermal scanning. Depending on the I2 partial pressure compounds can incorporate or release I2. On heating they undergo self-reduction. Some tungsten iodide clusters can be directly transferred into solution.

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

“…The black crystalline material W 6 I 22 was prepared according to the literature and can be handled in air . It dissolves in polar organic solvents like DMSO or acetone, obviously because the clusters are less tightly bridged within the structure of W 6 I 22 .…”

“…AE [W 6 I 14 ]: (a) From solution: W 6 I 22 was prepared according to the literature . The reaction of 50 mg (0.013 mmol) W 6 I 22 and ( AE )I (50 mmol) was carried out in acetone solution (50 mL) under air.…”

“…The preparation of ternary tungsten cluster compounds by means of solution chemistry has been impossible so far, because clusters like W 6 I 12 appear insoluble, obviously due to strong W–I (a–a) –W inter cluster coupling within layers of the W 6 I 12 structure , . With the recently discovered binary tungsten iodide W 6 I 22 this problem is no longer evident and the employment of W 6 I 22 can be a promising approach for room temperature reactions in solution and to target ligand exchanged cluster . In a preliminary attempt we present the preparation of the new AE [W 6 I 14 ] compounds with AE = Mg, Ca, Sr, and Ba via solid‐state and solution reactions.…”

Molybdenum Iodides – from Obscurity to Bright Luminescence

“…Of particular practical use in the synthesis of the {W 6 I 8 } 4+ clusters is the salt (Bu 4 N) 2 [W 6 I 14 ] , , , . Preparation of Cs 2 [W 6 I 14 ] from W 3 I 8 · 2I 2 and CsI at 550 °C can be recommended as alternative.…”

Synthesis of (TeI3)2[W6I14] via Iodination of WTe2

“…Our interest in the iodination of WTe 2 was stimulated by a recent report on the observation of binary WI 4 from this reaction . Nearly twenty phases have been reported to exist in the binary W–I system and a little less being confirmed . Tungsten iodides are thermally labile on heating because they are known to undergo self‐reduction by release of I 2 .…”