Chromium(II) chloride

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Chromium(II) chloride
3D model of chromium(II) chloride, green atom is chloride
Sample of chromium(II) chloride
Names
IUPAC name
Chromium(II) chloride
Other names
Chromous chloride
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.030.136 Edit this at Wikidata
EC Number
  • 233-163-3
RTECS number
  • GB5250000
UNII
UN number 3077
  • InChI=1S/2ClH.Cr/h2*1H;/q;;+2/p-2 checkY
    Key: XBWRJSSJWDOUSJ-UHFFFAOYSA-L checkY
  • 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
Appearance White 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]
115.3 J/mol·K[1]
Std enthalpy of
formation
(ΔfH⦵298)
 −395.4 kJ/mol[1]
−356 kJ/mol[1]
Hazards
GHS labelling:
GHS07: Exclamation mark[4]
Warning
H302, H315, H319, H335[4]
P261, P305+P351+P338[4]
NFPA 704 (fire diamond)
[5]
NFPA 704 four-colored diamondHealth 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).
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Chromium(II) chloride describes

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.

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

acetonitrile complex.[7]

Cr + n H2O + 2 HCl → CrCl2(H2O)n + H2

Structure and properties

Anhydrous CrCl2 is white

Jahn-Teller Effect.[8]

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

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]

References

  1. ^
    ISBN 978-1-4200-9084-0
    .
  2. ^
    doi:10.1107/S0365110X61002710
    .
  3. ^
    doi:10.1002/zaac.19734020206
    .
  4. ^ a b c Sigma-Aldrich Co., Chromium(II) chloride. Retrieved on 2014-07-04.
  5. ^ a b "MSDS of Chromium(II) chloride". fishersci.ca. Fisher Scientific. Retrieved 2014-07-04.
  6. ^
    ISBN 978-0121266011. {{cite book}}: |first= has generic name (help)CS1 maint: multiple names: authors list (link
    )
  7. ISBN 9780470132418
    .
  8. ISBN 978-0-08-037941-8
    .
  9. doi:10.1021/cr9703360
  10. doi:10.1039/C1SC00116G
    .
  11. doi:10.1021/ja00283a046
    .
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