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Vanadium(III) chloride
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Vanadium(III) chloride
Vanadium(III) chloride describes the inorganic compound with the formula VCl3 and its hydrates. It forms a purple anhydrous form and a green hexahydrate [VCl2(H2O)4]Cl·2H2O. These hygroscopic salts are common precursors to other vanadium(III) complexes and is used as a mild reducing agent.
VCl3 has the common layered BiI3 structure, a motif that features hexagonally closest-packed chloride framework with vanadium ions occupying the octahedral holes. VBr3 and VI3 adopt the same structure, but VF3 features a structure more closely related to ReO3. The V3+cation has a d2 electronic configuration with two unpaired electrons, making the compound paramagnetic. VCl3 is a Mott insulator and undergoes an antiferromagnetic transition at low temperatures.
Solid hexahydrate, [VCl2(H2O)4]Cl·2H2O, has a monoclinic crystal structure and consists of slightly distorted octahedral trans-[VCl2(H2O)4]+ centers as well as chloride and two molecules of water of crystallization. The hexahydrate phase loses two water of crystallization to form the tetrahydrate if heated to 90 °C in a stream of hydrogen chloride gas.
Solutions of vanadium(III) chloride in sulfuric acid and hydrochloric acid are used as electrolytes in vanadium redox batteries. It is also used as a mild Lewis acid in organic synthesis. One example of such is its use as a catalyst in the cleavage of the acetonide group. Another example of the use of VCl3 as a reducing agent is shown in the determination of nitrate and nitrite concentration in water, where VCl3 reduces nitrate to nitrite. This method is a safer alternative to the cadmium column method.
VCl3 is prepared by heating VCl4 at 160–170 °C under a flowing stream of inert gas, which sweeps out the Cl2. The bright red liquid converts to a purple solid.
The vanadium oxides can also be used to produce vanadium(III) chloride. For example, vanadium(III) oxide reacts with thionyl chloride at 200 °C:
The reaction of vanadium(V) oxide and disulfur dichloride also produces vanadium(III) chloride with the release of sulfur dioxide and sulfur.
The hexahydrate can be prepared by evaporation of acidic aqueous solutions of the trichloride.
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Vanadium(III) chloride
Vanadium(III) chloride describes the inorganic compound with the formula VCl3 and its hydrates. It forms a purple anhydrous form and a green hexahydrate [VCl2(H2O)4]Cl·2H2O. These hygroscopic salts are common precursors to other vanadium(III) complexes and is used as a mild reducing agent.
VCl3 has the common layered BiI3 structure, a motif that features hexagonally closest-packed chloride framework with vanadium ions occupying the octahedral holes. VBr3 and VI3 adopt the same structure, but VF3 features a structure more closely related to ReO3. The V3+cation has a d2 electronic configuration with two unpaired electrons, making the compound paramagnetic. VCl3 is a Mott insulator and undergoes an antiferromagnetic transition at low temperatures.
Solid hexahydrate, [VCl2(H2O)4]Cl·2H2O, has a monoclinic crystal structure and consists of slightly distorted octahedral trans-[VCl2(H2O)4]+ centers as well as chloride and two molecules of water of crystallization. The hexahydrate phase loses two water of crystallization to form the tetrahydrate if heated to 90 °C in a stream of hydrogen chloride gas.
Solutions of vanadium(III) chloride in sulfuric acid and hydrochloric acid are used as electrolytes in vanadium redox batteries. It is also used as a mild Lewis acid in organic synthesis. One example of such is its use as a catalyst in the cleavage of the acetonide group. Another example of the use of VCl3 as a reducing agent is shown in the determination of nitrate and nitrite concentration in water, where VCl3 reduces nitrate to nitrite. This method is a safer alternative to the cadmium column method.
VCl3 is prepared by heating VCl4 at 160–170 °C under a flowing stream of inert gas, which sweeps out the Cl2. The bright red liquid converts to a purple solid.
The vanadium oxides can also be used to produce vanadium(III) chloride. For example, vanadium(III) oxide reacts with thionyl chloride at 200 °C:
The reaction of vanadium(V) oxide and disulfur dichloride also produces vanadium(III) chloride with the release of sulfur dioxide and sulfur.
The hexahydrate can be prepared by evaporation of acidic aqueous solutions of the trichloride.
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