Chemistry:Nickel(II) bromide

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Nickel(II) bromide
Kristallstruktur Cadmiumiodid.png
NiBr2 powder.jpg
Anhydrous
Bromid nikelnatý.PNG
Hexahydrate
Names
IUPAC name
Nickel(II) bromide
Other names
Nickel dibromide,
Nickel bromide,
Nickelous bromide
Identifiers
3D model (JSmol)
ChemSpider
UNII
Properties
NiBr2
Molar mass 218.53 g/mol
Appearance yellow-brown crystals
Odor odorless
Density 5.10 g/cm3[1]
Melting point 963 °C (1,765 °F; 1,236 K) sublimes[1]
1.13 kg/L (0 °C)
1.22 kg/L (10 °C)
1.31 kg/L (20 °C)[1]
1.44 kg/L (40 °C)
1.55 kg/L (100 °C)[2]
Band gap 2.5 eV[3]
+5600.0·10−6 cm3/mol[4]
Structure[5]
hexagonal, hR9
R3m, No. 166
a = 0.36998 nm, c = 1.82796 nm
3
Thermochemistry[6]
−212.1 kJ·mol−1
Hazards
Main hazards Irritant, corrosive
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
1
0
Flash point Non-flammable
Related compounds
Other anions
nickel(II) fluoride
nickel(II) chloride
nickel(II) iodide
Other cations
cobalt(II) bromide
copper(II) bromide
palladium(II) 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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Infobox references

Nickel(II) bromide is the name for the inorganic compounds with the chemical formula NiBr2(H2O)x. The value of x can be 0 for the anhydrous material, as well as 2, 3, or 6 for the three known hydrate forms. The anhydrous material is a yellow-brown solid which dissolves in water to give blue-green hexahydrate (see picture).

Structure

The structure of the nickel bromides varies with the degree of hydration. In all of these cases, the nickel(II) ion adopts an octahedral molecular geometry. Similar structures are observed in aqueous solutions of nickel bromide.[7]

  • Anhydrous NiBr2 adopts the hexagonal cadmium chloride structure.[8] The interatomic distance for Ni-Br is 2.52—2.58 Å.[7] Anhydrous NiBr2 is a paramagnet at room temperature. Upon cooling, it turns into an antiferromagnet at 52 K, and then into a helimagnet at 22.8 K.[5]
  • The structure of the trihydrate has not been confirmed by X-ray crystallography. It is assumed to adopt a chain structure.[9]
  • The di- and hexahydrates adopt structures akin to those for the corresponding chlorides. The dihydrate consists of a linear chain, whereas the hexahydrate features isolated trans-[NiBr2(H2O)4] molecules together with two water molecules of crystallization.

Reactions and uses

NiBr2 has Lewis acid character, as indicated by its tendency to hydrate and form adducts with a variety of other Lewis bases.

NiBr2 is also used to prepare catalysts for cross-coupling reactions and various carbonylations.[8] NiBr2-glyme shows increased activity compared to NiCl2-glyme for some transformations.[10] File:NiBr2 scheme.tif

Safety

This compound is a suspected carcinogen.[11]

References

  1. 1.0 1.1 1.2 Haynes, p. 4.73
  2. nickel(II) bromide. chemister.ru
  3. Lee, Geunseop; Oh, S.-J. (1991). "Electronic structures of NiO, CoO, and FeO studied by 2pcore-level x-ray photoelectron spectroscopy". Physical Review B 43 (18): 14674–14682. doi:10.1103/PhysRevB.43.14674. PMID 9997359. Bibcode1991PhRvB..4314674L. 
  4. Haynes, p. 4.129
  5. 5.0 5.1 Nasser, J.A.; Kiat, J.M.; Gabilly, R. (1992). "X-ray investigation of magnetostriction in NiBr2". Solid State Communications 82 (1): 49–54. doi:10.1016/0038-1098(92)90404-W. Bibcode1992SSCom..82...49N. 
  6. Haynes, p. 5.29
  7. 7.0 7.1 Wakita, Hisanobu; Ichihashi, Mitsuyoshi; Mibuchi, Takeharu; Masuda, Isao (1982). "The Structure of Nickel(II) Bromide in Highly Concentrated Aqueous Solution by X-Ray Diffraction Analysis". Bulletin of the Chemical Society of Japan 55 (3): 817–821. doi:10.1246/bcsj.55.817. 
  8. 8.0 8.1 Luh, Tien-Yau; Kuo, Chi-Hong (2001-01-01). Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons, Ltd. doi:10.1002/047084289X.rn009. ISBN 9780470842898. 
  9. Defotis, G. C.; Goodey, J. R.; Narducci, A. A.; Welch, M. H. (1996). "NiBr2·3H2O, a lower dimensional antiferromagnet". Journal of Applied Physics 79 (8): 4718. doi:10.1063/1.361651. 
  10. Konev, Mikhail O.; Hanna, Luke E.; Jarvo, Elizabeth R. (2016-06-01). "Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides" (in en). Angewandte Chemie International Edition 55 (23): 6730–6733. doi:10.1002/anie.201601206. PMID 27099968. 
  11. "NICKEL BROMIDE | CAMEO Chemicals | NOAA". https://cameochemicals.noaa.gov/chemical/8879. 

Cited sources