Chromium(II) chloride

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Chromium(II) chloride
Rutile-unit-cell-3D-balls.png
Chromium(II) chloride.JPG
Names
IUPAC name
Chromium(II) chloride
Other names
Chromous chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.136 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 233-163-3
PubChem CID
RTECS number
  • GB5250000
UNII
UN number 3077
  • InChI=1S/2ClH.Cr/h2*1H;/q;;+2/p-2 Yes check.svgY
    Key: XBWRJSSJWDOUSJ-UHFFFAOYSA-L Yes check.svgY
  • InChI=1/2ClH.Cr/h2*1H;/q;;+2/p-2
    Key: XBWRJSSJWDOUSJ-NUQVWONBAQ
  • Cl[Cr]Cl
Properties
Cl2Cr
Molar mass 122.90 g·mol−1
AppearanceWhite to grey/green powder (anhydrous)
blue solid (tetrahydrate)
Odor Odorless
Density 2.88 g/cm3 (24 °C) [1]
Melting point 824 °C (1,515 °F; 1,097 K)
anhydrous
51 °C (124 °F; 324 K)
tetrahydrate, decomposes [1]
Boiling point 1,302 °C (2,376 °F; 1,575 K)
anhydrous [1]
Soluble [1]
Solubility Insoluble in alcohol, ether
Acidity (pKa)2
+7230·10−6 cm3/mol
Structure
Orthorhombic (deformed rutile, anhydrous), oP6 [2]
Monoclinic (tetrahydrate) [3]
Pnnm, No. 58 (anhydrous) [2]
P21/c, No. 14 (tetrahydrate) [3]
2/m 2/m 2/m (anhydrous) [2]
2/m (tetrahydrate) [3]
a = 6.64 Å, b = 5.98 Å, c = 3.48 Å (anhydrous) [2]
α = 90°, β = 90°, γ = 90°
Octahedral (Cr2+, anhydrous) [2]
Thermochemistry
71.2 J/mol·K [1]
Std molar
entropy (S⦵298)
115.3 J/mol·K [1]
−395.4 kJ/mol [1]
−356 kJ/mol [1]
Hazards
GHS labelling:
GHS-pictogram-exclam.svg [4]
Warning
H302, H315, H319, H335 [4]
P261, P305+P351+P338 [4]
NFPA 704 (fire diamond)
[5]
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
0
1
Lethal dose or concentration (LD, LC):
1870 mg/kg (rats, oral) [5]
Safety data sheet (SDS) Oxford MSDS
Related compounds
Other anions
Chromium(II) fluoride
Chromium(II) bromide
Chromium(II) iodide
Other cations
Chromium(III) chloride
Chromium(IV) chloride
Molybdenum(II) chloride
Tungsten(II) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Chromium(II) chloride describes inorganic compounds with the formula Cr Cl 2(H2O)n. The anhydrous solid is white when pure, however commercial samples are often grey or green; it is hygroscopic 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.

Contents

Synthesis

CrCl2 is produced by reducing chromium(III) chloride either with hydrogen at 500 °C:

2 CrCl3 + H2 → 2 CrCl2 + 2 HCl

or by electrolysis.

On the laboratory scale, LiAlH4, zinc, 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 with hydrogen chloride: [6]

Cr2(OAc)4 + 4 HCl → 2 CrCl2 + 4 AcOH

Treatment of chromium powder with concentrated hydrochloric acid gives a blue hydrated chromium(II) chloride, which can be converted to a related acetonitrile complex. [7]

Cr + n H2O + 2 HCl → CrCl2(H2O)n + H2

Structure and properties

Anhydrous CrCl2 is white [6] however commercial samples are often grey or green. It crystallizes in the Pnnm space group, which is an orthorhombically distorted variant of the rutile structure; making it isostructural to calcium chloride. The Cr centres are octahedral, being distorted by the Jahn-Teller Effect. [8]

Ball-and-stick model of chromium(II) chloride tetrahydrate. Chromium(II) chloride tetrahydrate.png
Ball-and-stick model of chromium(II) chloride tetrahydrate.

The hydrated derivative, CrCl2(H2O)4, forms monoclinic 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. [3]

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. [9] It is a reagent in the Nozaki-Hiyama-Kishi reaction, a useful method for preparing medium-size rings. [10] It is also used in the Takai olefination to form vinyl iodides from aldehydes in the presence of iodoform. [11]

Related Research Articles

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are available both in anhydrous and hydrated forms which are both hygroscopic. They are common sources of iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while the hydrate is a mild oxidizing agent. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2. It forms hydrates. Zinc chloride, anhydrous and its hydrates are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride. This salt is hygroscopic and even deliquescent. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

<span class="mw-page-title-main">Cerium(III) chloride</span> Chemical compound

Cerium(III) chloride (CeCl3), also known as cerous chloride or cerium trichloride, is a compound of cerium and chlorine. It is a white hygroscopic salt; it rapidly absorbs water on exposure to moist air to form a hydrate, which appears to be of variable composition, though the heptahydrate CeCl3·7H2O is known. It is highly soluble in water, and (when anhydrous) it is soluble in ethanol and acetone.

<span class="mw-page-title-main">Aluminium chloride</span> Chemical compound

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms a hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both the anhydrous form and the hexahydrate are colourless crystals, but samples are often contaminated with iron(III) chloride, giving them a yellow colour.

<span class="mw-page-title-main">Manganese(II) chloride</span> Chemical compound

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations.

<span class="mw-page-title-main">Chromium(III) chloride</span> Chemical compound

Chromium(III) chloride (also called chromic chloride) is an inorganic chemical compound with the chemical formula CrCl3. It forms several hydrates with the formula CrCl3·nH2O, among which are hydrates where n can be 5 (chromium(III) chloride pentahydrate CrCl3·5H2O) or 6 (chromium(III) chloride hexahydrate CrCl3·6H2O). The anhydrous compound with the formula CrCl3 are violet crystals, while the most common form of the chromium(III) chloride are the dark green crystals of hexahydrate, CrCl3·6H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

<span class="mw-page-title-main">Nickel(II) chloride</span> Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

<span class="mw-page-title-main">Tantalum(V) chloride</span> Chemical compound

Tantalum(V) chloride, also known as tantalum pentachloride, is an inorganic compound with the formula TaCl5. It takes the form of a white powder and is commonly used as a starting material in tantalum chemistry. It readily hydrolyzes to form tantalum(V) oxychloride (TaOCl3) and eventually tantalum pentoxide (Ta2O5); this requires that it be synthesised and manipulated under anhydrous conditions, using air-free techniques.

<span class="mw-page-title-main">Chromium(II) acetate</span> Chemical compound

Chromium(II) acetate hydrate, also known as chromous acetate, is the coordination compound with the formula Cr2(CH3CO2)4(H2O)2. This formula is commonly abbreviated Cr2(OAc)4(H2O)2. This red-coloured compound features a quadruple bond. The preparation of chromous acetate once was a standard test of the synthetic skills of students due to its sensitivity to air and the dramatic colour changes that accompany its oxidation. It exists as the dihydrate and the anhydrous forms.

<span class="mw-page-title-main">Chromium(III) fluoride</span> Chemical compound

Chromium(III) fluoride is an inorganic compound with the chemical formula CrF3. It forms several hydrates. The compound CrF3 is a green crystalline solid that is insoluble in common solvents, but the hydrates [Cr(H2O)6]F3 (violet) and [Cr(H2O)6]F3·3H2O (green) are soluble in water. The anhydrous form sublimes at 1100–1200 °C.

<span class="mw-page-title-main">Chromyl chloride</span> Chemical compound

Chromyl chloride is an inorganic compound with the formula CrO2Cl2. It is a reddish brown compound that is a volatile liquid at room temperature, which is unusual for transition metal compounds.

<span class="mw-page-title-main">Chromium compounds</span> Chemical compounds containing chromium

Chromium is a member of group 6, of the transition metals. The +3 and +6 states occur most commonly within chromium compounds, followed by +2; charges of +1, +4 and +5 for chromium are rare, but do nevertheless occasionally exist.

<span class="mw-page-title-main">Takai olefination</span>

Takai olefination in organic chemistry describes the organic reaction of an aldehyde with a diorganochromium compound to form an alkene. It is a name reaction, referencing Kazuhiko Takai, who first reported it in 1986. In the original reaction, the organochromium species is generated from iodoform or bromoform and an excess of chromium(II) chloride and the product is a vinyl halide. One main advantage of this reaction is the E-configuration of the double bond that is formed. According to the original report, existing alternatives such as the Wittig reaction only gave mixtures.

<span class="mw-page-title-main">Nozaki–Hiyama–Kishi reaction</span> Coupling reaction used in organic synthesis

The Nozaki–Hiyama–Kishi reaction is a nickel/chromium coupling reaction forming an alcohol from the reaction of an aldehyde with an allyl or vinyl halide. In their original 1977 publication, Tamejiro Hiyama and Hitoshi Nozaki reported on a chromium(II) salt solution prepared by reduction of chromic chloride by lithium aluminium hydride to which was added benzaldehyde and allyl chloride:

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3COCHCOCH−
3) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR′−). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5H
7O−
2 in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<span class="mw-page-title-main">Jones oxidation</span> Oxidation of alcohol

The Jones oxidation is an organic reaction for the oxidation of primary and secondary alcohols to carboxylic acids and ketones, respectively. It is named after its discoverer, Sir Ewart Jones. The reaction was an early method for the oxidation of alcohols. Its use has subsided because milder, more selective reagents have been developed, e.g. Collins reagent.

<span class="mw-page-title-main">Chromyl fluoride</span> Chemical compound

Chromyl fluoride is an inorganic compound with the formula CrO2F2. It is a violet-red colored crystalline solid that melts to an orange-red liquid.

<span class="mw-page-title-main">Chromium(II) fluoride</span> Chemical compound

Chromium(II) fluoride is an inorganic compound with the formula CrF2. It exists as a blue-green iridescent solid. Chromium(II) fluoride is sparingly soluble in water, almost insoluble in alcohol, and is soluble in boiling hydrochloric acid, but is not attacked by hot distilled sulfuric acid or nitric acid. Like other chromous compounds, chromium(II) fluoride is oxidized to chromium(III) oxide in air.

In organophosphorus chemistry, an aminophosphine is a compound with the formula R3−nP(NR2)n where R = H or an organic substituent, and n = 0, 1, 2. At one extreme, the parent H2PNH2 is lightly studied and fragile, but at the other extreme tris(dimethylamino)phosphine (P(NMe2)3) is commonly available. Intermediate members are known, such as Ph2PN(H)Ph. These compounds are typically colorless and reactive toward oxygen. They have pyramidal geometry at phosphorus.

<span class="mw-page-title-main">Transition metal pyridine complexes</span>

Transition metal pyridine complexes encompass many coordination complexes that contain pyridine as a ligand. Most examples are mixed-ligand complexes. Many variants of pyridine are also known to coordinate to metal ions, such as the methylpyridines, quinolines, and more complex rings.

References

  1. 1 2 3 4 5 6 7 8 Lide, David R., ed. (2009). CRC Handbook of Chemistry and Physics (90th ed.). Boca Raton, Florida: CRC Press. ISBN   978-1-4200-9084-0.
  2. 1 2 3 4 5 Tracy, Joseph W.; Gregory, N.W.; Lingafelter, E.C.; Dunitz, J.D.; Mez, H.-C.; Rundle, R.E.; Scheringer, Christian; Yakel, H.L.; Wilkinson, M.K. (1961). "The crystal structure of chromium(II) chloride". Acta Crystallographica. 4 (9): 927–929. doi: 10.1107/S0365110X61002710 .
  3. 1 2 3 4 Schnering, H.G. von; Brand, B.-H. (1973). "Struktur und Eigenschaften des blauen Chrom(II)-chlorid-tetrahydrats CrCl2.4H2O". Zeitschrift für anorganische und allgemeine Chemie. 402 (2): 159–168. doi:10.1002/zaac.19734020206.
  4. 1 2 3 Sigma-Aldrich Co., Chromium(II) chloride. Retrieved on 2014-07-04.
  5. 1 2 "MSDS of Chromium(II) chloride". fishersci.ca. Fisher Scientific. Retrieved 2014-07-04.
  6. 1 2 Riley, edited by Georg Brauer ; translated by Scripta Technica, Inc. Translation editor Reed F. (1963). Handbook of Preparative Inorganic Chemistry. Volume 1 (2nd ed.). New York, N.Y.: Academic Press. p. 1337. ISBN   978-0121266011.{{cite book}}: |first= has generic name (help)CS1 maint: multiple names: authors list (link)
  7. ↑ Holah, David G.; Fackler, John P. (1967). "Chromium(II) Salts and Complexes". Inorganic Syntheses. Inorganic Syntheses. Vol. 10. pp. 26–35. doi:10.1002/9780470132418.ch4. ISBN   9780470132418.
  8. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 1021–1022. ISBN   978-0-08-037941-8.
  9. ↑ (a) Kazuhiko Takai, K.; Loh, T.-P. "Chromium(II) Chloride" in Encyclopedia of Reagents for Organic Synthesis John Wiley & Sons: New York; 2005. doi : 10.1002/047084289X.rc166. (b) Alois Fürstner, "Carbon−Carbon Bond Formations Involving Organochromium(III) Reagents" Chemical Reviews, 1999, 99 (4), 991–1046 doi : 10.1021/cr9703360
  10. ↑ (a) MacMillan, D. W. C.; Overman, Larry E. "Enantioselective Total Synthesis of (−)-7-Deacetoxyalcyonin Acetate. First Synthesis of a Eunicellin Diterpene" J. Am. Chem. Soc. 1995, 117 (41), 10391–10392. doi : 10.1021/ja00146a028. (b) Lotesta, S. D.; Liu, J.; Yates, E. V.; Krieger, I.; Sacchettini, J. C.; Freundlich, J. S.; Sorensen, E. J. "Expanding the pleuromutilin class of antibiotics by de novo chemical synthesis" Chem. Sci. 2011, 2, 1258-1261. doi : 10.1039/C1SC00116G.
  11. ↑ 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. doi : 10.1021/ja00283a046.
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