Chromium(II) chloride describes

inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...

s with the

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...

Cr Cl₂(H₂O)_n. The anhydrous solid is white when pure, however commercial samples are often grey or green; it is

hygroscopic Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption (chemistry), absorption or adsorption from the surrounding Natural environment, environment, which is usually at normal or room temperature. If water mol ...

and readily dissolves in water to give bright blue air-sensitive solutions of the tetrahydrate Cr(H₂O)₄Cl₂. Chromium(II) chloride has no commercial uses but is used on a laboratory-scale for the synthesis of other chromium complexes.

Synthesis

CrCl₂ is produced by reducing

chromium(III) chloride Chromium(III) chloride (also called chromic chloride) is an inorganic chemical compound with the chemical formula . This crystalline salt forms several hydrates with the formula , among which are hydrates where ''n'' can be 5 (chromium(III) chlo ...

either with

hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...

at 500 °C: :2CrCl₃ + H₂ → 2CrCl₂ + 2HCl or by electrolysis. On the laboratory scale, LiAlH₄,

zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...

, and related reductants produce chromous chloride from chromium(III) precursors: :4 CrCl₃ + LiAlH₄ → 4 CrCl₂ + LiCl + AlCl₃ + 2 H₂ :2 CrCl₃ + Zn → 2 CrCl₂ + ZnCl₂ CrCl₂ can also be prepared by treating a solution of

chromium(II) acetate Chromium(II) acetate hydrate, also known as chromous acetate, is the coordination compound with the chemical formula, formula Cr2(CH3CO2)4(H2O)2. This formula is commonly abbreviated Cr2(OAc)4(H2O)2. This red-coloured compound features a quadruple ...

with

hydrogen chloride The Chemical compound, compound hydrogen chloride has the chemical formula and as such is a hydrogen halide. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hyd ...

: :Cr₂(OAc)₄ + 4 HCl → 2 CrCl₂ + 4 AcOH Treatment of chromium powder with concentrated

hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...

gives a blue hydrated chromium(II) chloride, which can be converted to a related acetonitrile complex. :Cr + nH₂O + 2HCl → CrCl₂(H₂O)_n + H₂

Structure and properties

Anhydrous CrCl₂ is white however commercial samples are often grey or green. It crystallizes in the ''Pnnm''

space group In mathematics, physics and chemistry, a space group is the symmetry group of a repeating pattern in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of the pattern that ...

, which is an orthorhombically distorted variant of the

rutile Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase, akaogiite, and brookite. Rutile has one of the highest refractive indices at vis ...

structure; making it isostructural to

calcium chloride Calcium chloride is an inorganic compound, a Salt (chemistry), salt with the chemical formula . It is a white crystalline solid at room temperature, and it is highly soluble in water. It can be created by neutralising hydrochloric acid with cal ...

. The Cr centres are

octahedral In geometry, an octahedron (: octahedra or octahedrons) is any polyhedron with eight faces. One special case is the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet at each vertex. Many types of i ...

, being distorted by the Jahn-Teller Effect. The hydrated derivative, CrCl₂(H₂O)₄, forms

monoclinic In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three Vector (geometric), vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in t ...

crystals with the ''P2₁/c'' space group. The molecular geometry is approximately octahedral consisting of four short Cr—O bonds (2.078 Å) arranged in a square planar configuration and two longer Cr—Cl bonds (2.758 Å) in a trans configuration.

Reactions

The reduction potential for Cr³⁺ + e⁻ ⇄ Cr²⁺ is −0.41. Since the reduction potential of H⁺ to H₂ in acidic conditions is +0.00, the chromous ion has sufficient potential to reduce acids to hydrogen, although this reaction does not occur without a catalyst.

Organic chemistry

Chromium(II) chloride is used as precursor to other inorganic and organometallic chromium complexes. Alkyl halides and nitroaromatics are reduced by CrCl₂. The moderate electronegativity of chromium and the range of substrates that CrCl₂ can accommodate make organochromium reagents very synthetically versatile. It is a reagent in the Nozaki-Hiyama-Kishi reaction, a useful method for preparing medium-size rings. It is also used in the Takai olefination to form vinyl iodides from aldehydes in the presence of

iodoform Iodoform (also known as triiodomethane) is the organoiodine compound with the chemical formula . It is a pale yellow, crystalline, volatile substance, with a penetrating and distinctive odor (in older chemistry texts, the smell is sometimes refe ...

.Simple and selective method for aldehydes (RCHO) -> (E)-haloalkenes (RCH:CHX) conversion by means of a haloform-chromous chloride system K. Takai, K. Nitta, K. Utimoto J. Am. Chem. Soc.; 1986; 108(23); 7408-7410. .

References

{{Chlorides Chromium(II) compounds Chlorides Metal halides Reducing agents