Chromium(III) chloride
Chromium 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 or 6. The anhydrous compound with the formula are violet crystals, while the most common form of the chromium chloride are the dark green crystals of hexahydrate,. Chromium chlorides find use as catalysts and as precursors to dyes for wool.
Structure
Anhydrous chromium chloride adopts the [Yttrium(III) chloride|] structure, with occupying one third of the octahedral interstices in alternating layers of a pseudo-cubic close packed lattice of ions. The absence of cations in alternate layers leads to weak bonding between adjacent layers. For this reason, crystals of cleave easily along the planes between layers, which results in the flaky appearance of samples of chromium chloride. The anhydrous is exfoliable down to the monolayer limit. If pressurized to 9.9 GPa it goes under a phase transition.Chromium(III) chloride hydrates
The hydrated chromium chlorides display the somewhat unusual property of existing in a number of distinct chemical forms, which differ in terms of the number of chloride anions that are coordinated to Cr and the water of crystallization. The different forms exist both as solids and in aqueous solutions. Several members are known of the series of. The common hexahydrate can be more precisely described as. It consists of the cation trans- and additional molecules of water and a chloride anion in the lattice. Two other hydrates are known, pale green and violet. Similar hydration isomerism is seen with other chromium compounds.Preparation
Anhydrous chromium chloride may be prepared by chlorination of chromium metal directly, or indirectly by carbothermic chlorination of chromium(III) oxide at 650–800 °CThe hydrated chlorides are prepared by treatment of chromate with hydrochloric acid and aqueous methanol.
Reactions
Slow reaction rates are common with chromium complexes. The low reactivity of the d3 ion can be explained using crystal field theory. One way of opening up to substitution in solution is to reduce even a trace amount to, for example using zinc in hydrochloric acid. This chromium compound undergoes substitution easily, and it can exchange electrons with via a chloride bridge, allowing all of the to react quickly. With the presence of some chromium, solid dissolves rapidly in water. Similarly, ligand substitution reactions of solutions of are accelerated by chromium catalysts.With molten alkali metal chlorides such as potassium chloride, gives salts of the type and, which is also octahedral but where the two chromiums are linked via three chloride bridges.
The hexahydrate can also be dehydrated with thionyl chloride:
Complexes with organic ligands
is a Lewis acid, classified as "hard" according to the Hard-Soft Acid-Base theory. It forms a variety of adducts of the type, where L is a Lewis base. For example, it reacts with pyridine to form the pyridine complex:Treatment with trimethylsilylchloride in THF gives the anhydrous THF complex:
Precursor to organochromium complexes
Chromium chloride is used as the precursor to many organochromium compounds, for example bis(benzene)chromium, an analogue of ferrocene:Phosphine complexes derived from catalyse the trimerization of ethylene to 1-hexene.
Use in organic synthesis
One niche use of in organic synthesis is for the in situ preparation of chromium(II) chloride, a reagent for the reduction of alkyl halides and for the synthesis of -alkenyl halides. The reaction is usually performed using two moles of per mole of lithium aluminium hydride, although if aqueous acidic conditions are appropriate zinc and hydrochloric acid may be sufficient.Chromium chloride has also been used as a Lewis acid in organic reactions, for example to catalyse the nitroso Diels-Alder reaction.