Copper(II) chloride - Wikipedia, the free encyclopedia http://en.wikipedia.

org/wiki/Cucl2

Copper(II) chloride
From Wikipedia, the free encyclopedia
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Copper(II) chloride is the chemical Copper(II) chloride

compound with the formula CuCl2.
This is a light brown solid, which
slowly absorbs moisture to form a
blue-green dihydrate. The copper(II)
chlorides are some of the most
common copper(II) compounds, after
copper sulfate.

Contents
1 Structure
2 Properties and reactions
3 Preparation
3.1 Natural occurrence
4 Uses
4.1 Co-catalyst in Wacker
Process IUPAC name
4.2 Chlorinations Copper(II) chloride
4.3 Other organic Copper dichloride
synthetic applications Other names
4.4 Niche uses Cupric chloride
5 Safety Identifiers
6 References CAS number 7447-39-4 ,
7 Further reading 10125-13-0 (dihydrate)
8 External links PubChem 169664
ChemSpider 148374
UNII P484053J2Y
Structure RTECS GL7000000
number
Anhydrous CuCl2 adopts a distorted SMILES
cadmium iodide structure. In this Cl[Cu]Cl
motif, the copper centers are
[Cu+2].[Cl-].[Cl-]
octahedral. Most copper(II)
compounds exhibit distortions from InChI
idealized octahedral geometry due to InChI=1S/2ClH.Cu/h2*1H;/q;;+2/p-2
the Jahn-Teller effect, which in this

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case describes the localization of one

Key: ORTQZVOHEJQUHG-UHFFFAOYSA-L
d-electron into a molecular orbital
that is strongly antibonding with InChI=1/2ClH.Cu/h2*1H;/q;;+2/p-2/rCl2Cu
respect to a pair of chloride ligands. /c1-3-2
In CuCl2·2H2O, the copper again Key: ORTQZVOHEJQUHG-LRIOHBSEAE
adopts a highly distorted octahedral
geometry, the Cu(II) centers being InChI=1/2ClH.Cu/h2*1H;/q;;+2/p-2
surrounded by two water ligands and Key: ORTQZVOHEJQUHG-NUQVWONBAE
four chloride ligands, which bridge Properties
[1] Molecular CuCl 2
asymmetrically to other Cu centers.
formula
Copper(II) chloride is paramagnetic. Molar mass 134.45 g/mol (anhydrous)
170.48 g/mol (dihydrate)
Of historical interest, CuCl2·2H2O was
used in the first electron Appearance yellow-brown solid
(anhydrous)
paramagnetic resonance
blue-green solid (dihydrate)
measurements by Yevgeny Zavoisky in
[2][3] Density 3.386 g/cm3 (anhydrous)
1944.
2.51 g/cm3 (dihydrate)
Melting
Properties and point 498 °C (anhydrous)
100 °C (dehydration of
reactions dihydrate)

Aqueous Boiling point

993 °C (anhydrous, decomp)
solution
prepared Solubility in 70.6 g/100 mL (0 °C)
from water 75.7 g/100 mL (25 °C)
copper(II) Structure
chloride Crystal distorted CdI2 structure
contain a structure
range of Coordination Octahedral
copper(II) geometry
Aqueous solutions of
complexes Hazards
"copper(II) chloride".
depending MSDS Fischer Scientific
Greenish when high on on (https://fscimage.fishersci.com
[Cl −], more blue when /msds/05625.htm)
lower on [Cl −]. EU Not listed
classification
concentration, temperature,and the NFPA 704
presence of additional chloride ions. 0
These species include blue color of 2 1
2+
[Cu(H2O)6] and yellow or red color
of the halide complexes of the formula Flash point Non-flammable
x− [4]
[CuCl2+x ] . Related compounds

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It Other anions Copper(II) fluoride

Copper(II) bromide
Other Copper(I) chloride
cations Silver chloride
Gold(III) chloride
(what is this?) (verify)
Except where noted otherwise, data are
given for materials in their standard state
(at 25 °C, 100 kPa)
Copper(II) chloride Infobox references
dihydrate crystal
decomposes to CuCl and Cl2 at 1000 °C:

2 CuCl2 → 2 CuCl + Cl2

It reacts with HCl or other chloride sources to form complex ions: the red
− 2− [5]
CuCl3 , and the yellow CuCl4 .

− 2−
CuCl2 + 2 Cl− CuCl3 + Cl− CuCl4

Some of these complexes can be crystallized from aqueous solution, and they
adopt a wide variety of structural types (Fig. 1).

Copper(II) hydroxide precipitates upon treating copper(II) chloride solutions

with base:

CuCl2 + 2 NaOH → Cu(OH)2 + 2 NaCl

Copper(II) chloride also forms a variety of coordination complexes with ligands

such as pyridine and triphenylphosphine oxide:

CuCl2 + 2 C5H5N → [CuCl2(C5H5N)2] (tetragonal)

CuCl2 + 2 (C6H5)3P=O → [CuCl2((C6H5)3P=O)2] (tetrahedral)

However "soft" ligands such as phosphines (e.g., triphenylphosphine), iodide,

and cyanide as well as some tertiary amines cause reduction to give copper(I)

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complexes. To convert copper(II) chloride to copper(I) derivatives it is generally

more convenient to reduce an aqueous solution with sulfur dioxide as the
reductant:

2 CuCl2 + SO2 + 2 H2O → 2 CuCl + 2 HCl + H2SO4

Hydrolysis give the copper oxychloride, Cu2Cl(OH)3, a popular fungicide.

Preparation
Copper(II) chloride is prepared commercially by the action of chlorination of
copper:

Cu + Cl2 + 2 H2O → CuCl2(H2O)2

It can also be generated by treatment of the hydroxide, oxide, or copper(II)

carbonate with hydrochloric acid. Electrolysis of aqueous sodium chloride with
copper electrodes produces (among other things) a blue-green foam that can be
collected and converted to the hydrate.

Anhydrous CuCl2 may be prepared directly by union of the elements, copper and
chlorine.

CuCl2 may be purified by crystallization from hot dilute hydrochloric acid, by

[6][7]
cooling in a CaCl2-ice bath.

Natural occurrence

Copper(II) chloride occurs naturally as the very rare mineral tolbachite and the
dihydrate eriochalcite. Both are found near fumaroles. More common are mixed
oxyhydroxide-chlorides like atacamite Cu2(OH)3Cl, arising among Cu ore beds
oxidation zones in arid climate (also known from some altered slags).

Uses
Co-catalyst in Wacker Process

A major industrial application for copper(II) chloride is as a co-catalyst with

palladium(II) chloride in the Wacker process. In this process, ethene (ethylene)
is converted to ethanal (acetaldehyde) using water and air. During the reaction,
PdCl2 is reduced to Pd, and the CuCl2 serves to re-oxidize this back to PdCl2. Air
can then oxidize the resultant CuCl back to CuCl2, completing the cycle.

1. C2H4 + PdCl2 + H2O → CH3CHO + Pd + 2 HCl

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2. Pd + 2 CuCl2 → 2 CuCl + PdCl2

3. 4 CuCl + 4 HCl + O2 → 4 CuCl2 + 2 H2O

The overall process is:

2 C2H4 + O2 → 2 CH3CHO

Chlorinations

Copper(II) chloride catalyzes the chlorination in the production of vinyl chloride

[8]
and dichloroethane.

Other organic synthetic applications

Copper(II) chloride has a variety of specialized applications in the synthesis of

[6]
organic compounds. It effects chlorination of aromatic hydrocarbons- this is
often performed in the presence of aluminium oxide. It is able to chlorinate the
[9]
alpha position of carbonyl compounds:

This reaction is performed in a polar solvent such as dimethylformamide (DMF),

often in the presence of lithium chloride, which accelerates the reaction.

CuCl2, in the presence of oxygen, can also oxidize phenols. The major product
can be directed to give either a quinone or a coupled product from oxidative
[10]
dimerization. The latter process provides a high-yield route to 1,1-binaphthol:

Such compounds are intermediates in the synthesis of BINAP and its derivatives

Copper(II) chloride dihydrate promotes the hydrolysis of acetonides, i.e., for

[11]
deprotection to regenerate diols or aminoalcohols, as in this example (where
[12]
TBDPS = tert-butyldiphenylsilyl):

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CuCl2 also catalyses the free radical addition of sulfonyl chlorides to alkenes; the
alpha-chlorosulfone may then undergo elimination with base to give a vinyl
[citation needed]
sulfone product.

Niche uses

Copper(II) chloride is also used in pyrotechnics as a blue/green coloring agent.

In a flame test, copper chlorides, like all copper compounds, emit green-blue.

Safety
It is toxic and only concentrations below 5 ppm are allowed in drinking water by
the US Environmental Protection Agency.

References
1. ^ Wells, A.F. (1984) Structural Heinemann. ISBN 0-7506-3365-4.
Inorganic Chemistry, Oxford: 5. ^ Naida S. Gill et al. (1967).
Clarendon Press. ISBN "Tetrahalo Complexes of Dipositive
0-19-855370-6. Metals in the First Transition
2. ^ Peter Baláž (2008). Series". Inorg. Synth. 9: 136–142.
Mechanochemistry in Nanoscience doi:10.1002/9780470132401.ch37
and Minerals Engineering (http://dx.doi.org
(http://books.google.com /10.1002%2F9780470132401.ch37) .
/?id=FldqbSffUMgC&pg=PA167) . 6. ^ a b S. H. Bertz, E. H. Fairchild, in
Springer. p. 167. ISBN 3540748547. Handbook of Reagents for Organic
http://books.google.com Synthesis, Volume 1: Reagents,
/?id=FldqbSffUMgC&pg=PA167. Auxiliaries and Catalysts for C-C
3. ^ Marina Brustolon (2009). Electron Bond Formation, (R. M. Coates, S. E.
paramagnetic resonance: a Denmark, eds.), pp. 220-3, Wiley,
practitioner's toolkit New York, 1999.
(http://books.google.com 7. ^ W. L. F. Armarego, Christina Li Lin
/?id=l3F9yUSk-rgC&pg=PA3) . John Chai (2009-05-22) (Google Books
Wiley and Sons. p. 3. excerpt). Purification of Laboratory
ISBN 0470258829. Chemicals (http://books.google.com
http://books.google.com /?id=PTXyS7Yj6zUC&pg=PA461) (6th
/?id=l3F9yUSk-rgC&pg=PA3. ed.). Butterworth-Heinemann.
4. ^ Greenwood, N. N.; & Earnshaw, A. pp. 461. ISBN 1856175677.
(1997). Chemistry of the Elements http://books.google.com
(2nd Edn.), Oxford:Butterworth- /?id=PTXyS7Yj6zUC&pg=PA461.

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Copper(II) chloride - Wikipedia, the free encyclopedia http://en.wikipedia.org/wiki/Cucl2

8. ^ H.Wayne Richardson, "Copper 6682-7) .

Compounds" in Ullmann's 11. ^ Chandrasekhar, M.; Kusum L.
Encyclopedia of Industrial Chemistry, Chandra, and Vinod K. Singh (2003).
2005, Wiley-VCH, Weinheim, "Total Synthesis of (+)-Boronolide,
doi:10.1002/14356007.a07_567 (+)-Deacetylboronolide, and
(http://dx.doi.org (+)-Dideacetylboronolide". Journal of
/10.1002%2F14356007.a07_567) Organic Chemistry 68 (10):
9. ^ C. E. Castro, E. J. Gaughan, D. C. 4039–4045. doi:10.1021/jo0269058
Owsley (1965). "Cupric Halide (http://dx.doi.org
Halogenations". Journal of Organic /10.1021%2Fjo0269058) .
Chemistry 30: 587. PMID 12737588
doi:10.1021/jo01013a069 (http://www.ncbi.nlm.nih.gov/pubmed
(http://dx.doi.org /12737588) .
/10.1021%2Fjo01013a069) . 12. ^ Krishna, Palakodety Radha; G.
10. ^ J. Brussee, J. L. G. Groenendijk, J. Dayaker (2007). "A stereoselective
M. Koppele, A. C. A. Jansen (1985). total synthesis of (-)-andrachcinidine
"On the mechanism of the formation via an olefin cross-metathesis
of s(−)-(1, 1'-binaphthalene)-2,2'-diol protocol". Tetrahedron Letters
via copper(II)amine complexes". (Elsevier) 48: 7279–7282.
Tetrahedron 41: 3313. doi:10.1016/j.tetlet.2007.08.053
doi:10.1016/S0040-4020(01)96682-7 (http://dx.doi.org
(http://dx.doi.org /10.1016%2Fj.tetlet.2007.08.053) .
/10.1016%2FS0040-4020%2801%299

Further reading
1. Greenwood, Norman N.; Earnshaw, Alan. (1997), Chemistry of the Elements
(2nd ed.), Oxford: Butterworth-Heinemann, ISBN 0080379419
2. Lide, David R. (1990). CRC handbook of chemistry and physics: a ready-
reference book of chemical and physical data. Boca Raton: CRC Press.
ISBN 0-8493-0471-7.
3. The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA,
1960.
4. D. Nicholls, Complexes and First-Row Transition Elements, Macmillan Press,
London, 1973.
5. A. F. Wells, 'Structural Inorganic Chemistry, 5th ed., Oxford University
Press, Oxford, UK, 1984.
6. J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York,
1992.
7. Fieser & Fieser Reagents for Organic Synthesis Volume 5, p158, Wiley, New
York, 1975.
8. D. W. Smith (1976). "Chlorocuprates(II)". Coordination Chemistry Reviews
21 (2-3): 93–158. doi:10.1016/S0010-8545(00)80445-2 (http://dx.doi.org
/10.1016%2FS0010-8545%2800%2980445-2) .

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External links
Copper (II) Chloride - Description and Pictures
(http://www.amazingrust.com/Experiments/background_knowledge
/CuCl2.html)
National Pollutant Inventory - Copper and compounds fact sheet
(http://www.npi.gov.au/database/substance-info/profiles/27.html)
Retrieved from "http://en.wikipedia.org/wiki/Copper(II)_chloride"
Categories: Copper compounds | Chlorides | Metal halides | Semiconductor
materials | Coordination compounds | Pyrotechnic colorants

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