Copper(I) bromide
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Names | |
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Other names
Cuprous bromide
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Identifiers | |
3D model (JSmol)
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ChemSpider | |
ECHA InfoCard | 100.029.210 |
PubChem CID
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UNII | |
CompTox Dashboard (EPA)
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Properties | |
CuBr | |
Molar mass | 143.45 g/mol |
Appearance | white powder (see text) |
Density | 4.71 g/cm3, solid |
Melting point | 492 °C (918 °F; 765 K) |
Boiling point | 1,345 °C (2,453 °F; 1,618 K) |
slightly soluble | |
Solubility | soluble in HCl, HBr, ammonium hydroxide, acetonitrile negligible in acetone, sulfuric acid |
-49.0·10−6 cm3/mol | |
Refractive index (nD)
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2.116 |
1.46 D | |
Hazards | |
Flash point | Non-flammable |
NIOSH (US health exposure limits): | |
PEL (Permissible)
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TWA 1 mg/m3 (as Cu)[1] |
REL (Recommended)
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TWA 1 mg/m3 (as Cu)[1] |
IDLH (Immediate danger)
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TWA 100 mg/m3 (as Cu)[1] |
Related compounds | |
Other anions
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Copper(I) chloride Copper(I) iodide |
Other cations
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Silver(I) bromide Copper(II) bromide Mercury(I) bromide |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Copper(I) bromide is the chemical compound with the formula CuBr. This diamagnetic solid adopts a polymeric structure akin to that for zinc sulfide. The compound is widely used in the synthesis of organic compounds and as a lasing medium in copper bromide lasers.
Preparation, basic properties, structure
The compound is white, although samples are often colored due to the presence of copper(II) impurities.[2] The copper(I) ion also oxidizes easily in air. It is commonly prepared by the reduction of cupric salts with sulfite in the presence of bromide.[3] For example, the reduction of copper(II) bromide with sulfite yields copper(I) bromide and hydrogen bromide:
- 2 CuBr2 + H2O + SO32− → 2 CuBr + SO42− + 2 HBr
CuBr is insoluble in most solvents due to its polymeric structure, which features four-coordinated, tetrahedral Cu centers interconnected by bromide ligands (ZnS structure). Upon treatment with Lewis bases, CuBr converts to molecular adducts. For example, with dimethyl sulfide, the colorless complex is formed:[4]
- CuBr + S(CH3)2 → CuBr(S(CH3)2)
In this coordination complex, the copper is two-coordinate, with a linear geometry. Other soft ligands afford related complexes. For example, triphenylphosphine gives CuBr(P(C6H5)3), although this species has a more complex structure. Thermal excitation of copper(I) bromide vapour yields a blue violet emission which is of greater saturation than known copper(I) chloride emission.[5] Copper(I) bromide is hence an advantageous emitter in pyrotechnic flames.
Applications in organic chemistry
In the Sandmeyer reaction, CuBr is employed to convert diazonium salts into the corresponding aryl bromides:[3]
- ArN2+ + CuBr → ArBr + N2 + Cu+
The aforementioned complex CuBr(S(CH3)2) is widely used to generate organocopper reagents.[4] Related CuBr complexes are catalysts for Atom Transfer Radical Polymerization and Cu-catalyzed Cross-Dehydrogenative Couplings (CDC).
References
- ^ a b c NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
- ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
- ^ a b This report gives a procedure for generating CuBr: Jonathan L. Hartwell (1955). "o-Chlorobromobenzene". Organic Syntheses; Collected Volumes, vol. 3, p. 185..
- ^ a b Jarowicki, K.; Kocienski, P. J.; Qun, L. "1,2-Metallate Rearrangement: (Z)-4-(2-Propenyl)-3-Octen-1-ol" Organic Syntheses, Collected Volume 10, p.662 (2004).http://www.orgsyn.org/orgsyn/pdfs/V79P0011.pdf
- ^ E.-C. Koch, Spectral Investigation and Color Properties of Copper(I) Halides CuX (X=F, Cl, Br, I) in Pyrotechnic Combustion Flames, Propellants Explos. Pyrotech. 2015, 40, 798-802.[1]
External links
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