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Vanadium(III) bromide

Vanadium(III) bromide, also known as vanadium tribromide, describes the inorganic compounds with the formula VBr<sub>3</sub> and its hydrates. The anhydrous material is a green-black solid. In terms of its structure, the compound is polymeric with octahedral vanadium(III) surrounded by six bromide ligands.

Preparation

VBr<sub>3</sub> has been prepared by treatment of vanadium tetrachloride with hydrogen bromide:

:2 VCl<sub>4</sub> + 8 HBr → 2 VBr<sub>3</sub> + 8 HCl + Br<sub>2</sub>

The reaction proceeds via the unstable vanadium(IV) bromide (VBr<sub>4</sub>), which releases Br<sub>2</sub> near room temperature.

It is also possible to prepare vanadium(III) bromide by reacting bromine with vanadium or ferrovanadine:

: 2 V + 3 Br<sub>2</sub> → 2 VBr<sub>3</sub>
:2 VFe + 6 Br<sub>2</sub> → 2 VBr<sub>3</sub> + FeBr<sub>3</sub>

Properties

Physical

Vanadium(III) bromide is present in the form of black, leafy, very hygroscopic crystals with a sometimes greenish sheen. It is soluble in water with green color. Its crystal structure is isotypic to that of vanadium(III) chloride with space group Rc (space group no. 167), a = 6.400 Å, c = 18.53 Å. When heated to temperatures of around 500&nbsp;°C, a violet gas phase is formed, from which, under suitable conditions, red vanadium(IV) bromide can be separated by rapid cooling, which decomposes at −23&nbsp;°C.

Chemical

Like vanadium(III) chloride, vanadium(III) bromide forms red-brown soluble complexes with dimethoxyethane and THF, such as mer-VBr<sub>3</sub>(THF)<sub>3</sub>.

Aqueous solutions prepared from VBr<sub>3</sub> contain the cation trans-[VBr<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]<sup>+</sup>. Evaporation of these solutions give the salt trans-[VBr<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]Br<sup>.</sup>(H<sub>2</sub>O)<sub>2</sub>.

Further reading

  • Stebler, A.; Leuenberger, B.; Guedel, H. U. "Synthesis and crystal growth of A<sub>3</sub>M<sub>2</sub>X<sub>9</sub> (A = Cs, Rb; M = Ti, V, Cr; X = Cl, Br)" Inorganic Syntheses (1989), volume 26, pages 377–85.

References