Copper(I) chloride

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Copper(I) chloride
Copper(I) chloride (quite
commonly called cuprous
chloride), is the lower
chloride of copper, with the
formula CuCl. It occurs
naturally as the mineral
nantokite. It is a white solid
which is almost insoluble in
water, and which tends to
oxidise in air to green CuCl2.
It is a Lewis acid which reacts
with suitable ligands such as
ammonia or chloride ion to
form complexes, many of
which are water-soluble. It is General
even able to form a stable
complex with carbon Systematic name Copper(I) chloride
monoxide. Other names Cuprous chloride
In aqueous solution, CuCl Molecular formula CuCl
would be unstable with
Molar mass 98.99 g/mol
respect to disproportionation
into Cu and CuCl2, but its low white powder, slightly
Appearance
solubility allows it to be a green from oxidation
stable compound.
CAS number [7758-89-6]
Properties
Chemical
Density and phase 4.140 g/cm3, solid
Properties
Solubility in water 0.0062 g/100 ml (20 °C)
Copper(I) chloride is a Lewis in ethanol insoluble
acid, classified as soft
according to the Hard-Soft in hydrochloric acid
Acid-Base concept. Thus it in diethyl ether soluble
tends to form stable in aqueous ammonia
complexes with soft Lewis
Melting point 430 °C (703 K)
bases such as
triphenylphosphine: 1490 °C (1760 K),
Boiling point
decomposes
CuCl + PPh3 → [CuCl(PPh3)]4
(Ph = phenyl) Structure
Tetrahedral close packed
Although CuCl is insoluble in Crystal structure
( Zinc blende structure)
water, it dissolves in aqueous
solutions containing suitable Dipole moment ?D
donor molecules. It readily
forms complexes with halide Hazards
ions, for example forming
H3O+ CuCl2- with MSDS External MSDS
concentrated hydrochloric
Main hazards Irritant
acid. It also dissolves readily
in solutions containing CN-,
S2O32- or NH3 NFPA 704

Solutions of CuCl in HCl or

NH3 absorb carbon monoxide
to form colourless complexes
such as the crystalline
halogen-bridged dimer
[CuCl(CO)]2. The same HCl
solution can also react with
acetylene gas to form
[CuCl(C2H2)], while an NH3
solution of CuCl forms an
explosive acetylide with
acetylene. Complexes of CuCl
with alkenes can be made by
reduction of CuCl2 by sulfur
dioxide in the presence of the
alkene in alcohol solution.
Complexes with chelating
alkenes such as
1,5-cyclooctadiene are
particularly stable:
Flash point n/a
R/S statement R: 22, 50, 53 S: 22, 60/61
RTECS number GL6990000
Supplementary data page
Structure & properties n, εr, etc.
Phase behaviour
Thermodynamic data
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Related compounds
Copper(I) bromide
Other anions
Copper(I) iodide
Copper(II) chloride
Other cations
Silver(I) chloride
Except where noted otherwise, data are given for
materials in their standard state (at 25°C, 100 kPa)
Infobox disclaimer and references

CuCl reacts with organometallic compounds such as methyllithium (CH3Li) to form

"Gilman reagents" such as (CH3)2CuLi, which find extensive use in organic
synthesis. Grignard reagents react similarly.

Preparation
Copper(I) chloride may be prepared by the reduction of copper(II) salts such as
CuSO4 using sulfur dioxide or copper metal. SO2 may be prepared in situ from
sodium bisulfite (NaHSO3) or sodium metabisulfite (Na2S2O5) and acid. The
reduction is carried out in hydrochloric acid, and the resulting CuCl2- complex is
diluted to precipitate white CuCl (by driving the equilibrium using Le Chatelier's
principle).

(1) NaHSO3( aq) + HCl ( aq) → SO2( aq) + NaCl + H2O( l)

(2) 2 CuSO4( aq) + SO2( aq) + 2 H2O( l) + 4 HCl( aq) → 2 HCuCl2( aq) + 3 H2SO4(
aq)
(3) HCuCl2( aq) + H2O( l) → CuCl( s) + H3O+( aq) + Cl-( aq)

Uses
A major chemical use for copper(I) chloride is as a catalyst for a variety of
organic reactions. Compared to other "soft" Lewis acids, it is much more
affordable than non-toxic silver(I) chloride and palladium(II) chloride, and much
less toxic than lead(II) chloride and mercury(II) chloride. In addition, it can
undergo redox chemistry via copper(II) or copper(III) intermediates. This
combination of properties make copper(I) salts invaluable reagents.

One such application is in the Sandmeyer reaction. Treatment of an

arenediazonium salt with CuCl leads to an aryl chloride, for example:

The reaction has wide scope, and usually gives good yields.

The observation that copper(I) halides catalyse 1,4-addition of Grignard reagents

to alpha,beta-unsaturated ketones led to the development of organocuprate
reagents that are widely used today in organic synthesis :

Although other copper(I) compounds such as copper(I) iodide are now more often
used for this type of reaction, there are cases where copper(I) chloride is
particularly effective:

Here, Bu indicates an n- butyl group. Without CuCl, the Grignard reagent alone
gives a mixture of 1,2 and 1,4-addition products (i.e., the butyl adds at the closer
to the C=O).

Copper(I) chloride is also an intermediate formed from copper(II) chloride in the

Wacker process.

Precautions
Copper salts do have some toxicity and should be handled with care; wear gloves
and goggles. Avoid bringing CuCl into contact with alkynes.
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