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Copper(i) Chloride Overview 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 even able to form a stable complex with carbon monoxide. In aqueous solution, CuCl would be unstable with respect to disproportionation into Cu and CuCl2, but its low solubility allows it to be a stable compound1. Chemical Properties Copper(I) chloride is a Lewis acid, classified as soft according to the Hard-Soft Acid-Base theory. Thus it tends to form stable complexes with soft Lewis bases such as triphenylphosphine: CuCl + PPh3 → CuCl(PPh3)4 (Ph = phenyl) Although CuCl is insoluble in water, it dissolves in aqueous solutions containing suitable donor molecules. It readily forms complexes with halide ions, for example forming H3O+ CuCl2- with concentrated hydrochloric acid. It also dissolves readily in solutions containing CN-, S2O32- or NH3 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 stable4: 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 hydrogen sulfite (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 reaction5. 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 ketones6 led to the development of organocuprate reagents that are widely used today in organic synthesis 7: 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 effective8: 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, wearing gloves and goggles. Avoid bringing CuCl into contact with alkynes. Suppliers/Manufacturers Template: inorganic_stylesheet1 References - N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, Oxford, UK, 1997.
- Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann Arbor, Michigan, 1990.
- The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
- D. Nicholls, Compleses and First-Row Transition Elements, Macmillan Press, London, 1973.
- (a) L. G. Wade, Organic Chemistry, 5th ed., p. 871, Prentice Hall, Upper Saddle RIver, New Jersey, 2003. (b) J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York, 1992.
- M. S. Kharasch, P. O. Tawney, Journal of the American Chemical Society, 63, 2308 (1941).
- J. T. B. H. Jasrzebski, G. van Koten, in Modern Organocopper Chemistry, (N. Krause, ed.), p. 1, Wiley-VCH, Weinheim, Germany, 2002.
- (a) S. H. Bertz, E. H. Fairchild, in Handbook of Reagents for Organic Synthesis, Volume 1: Reagents, Auxiliaries and Catalysts for C-C Bond Formation, (R. M. Coates, S. E. Denmark, eds.), pp. 220-3, Wiley, New York, 1999. (b) J. Munch-Petersen et al., Acta Chimica Scand., 15, 277 (1961).
- A. F. Wells, 'Structural Inorganic Chemistry, 5th ed., Oxford University Press, Oxford, UK, 1984.
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