Vanadium(II) chloride is the inorganic compound with the formula VCl<sub>2</sub>, and is the most reduced vanadium chloride. Vanadium(II) chloride is an apple-green solid that dissolves in water to give purple solutions.
VCl<sub>2</sub> dissolves in water to give the purple hexaaquo ion [V(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup>. Evaporation of such solutions produces crystals of [V(H<sub>2</sub>O)<sub>6</sub>]Cl<sub>2</sub>.
Solid VCl<sub>2</sub> adopts the cadmium iodide structure, featuring octahedral coordination geometry. VBr<sub>2</sub> and VI<sub>2</sub> are structurally and chemically similar to the dichloride. All have the d<sup>3</sup> configuration, with a quartet ground state, akin to Cr(III).
Solid VCl<sub>2</sub> is prepared by disproportionation of vanadium trichloride, which leaves a residue of VCl<sub>2</sub> after evaporation of the tetrachloride:
The trichloride can also be reduced by heating under flowing hydrogen:
Vanadium dichloride is used as a specialty reductant in organic chemistry. As an aqueous solution, it converts cyclohexylnitrate to cyclohexanone. It reduces phenyl azide into aniline.