Chemistry:Zirconium(IV) bromide

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Zirconium(IV) bromide
Names
Other names
zirconium tetrabromide
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 237-417-4
Properties
ZrBr4
Molar mass 410.86 g/mol
Appearance off-white powder
Density 4.201 g/cm3, solid
Melting point 450 °C (842 °F; 723 K)
Boiling point sublimes
reacts with water
Structure
Cubic, cP40
P-43m, No. 205
Hazards
GHS pictograms GHS05: Corrosive
GHS Signal word Danger
H314
P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P363, P405, P501
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
3
2
Related compounds
Other anions
Zirconium(IV) fluoride
Zirconium(IV) chloride
Zirconium(IV) iodide
Other cations
Titanium tetrabromide
Hafnium tetrabromide
Related compounds
Zirconium(III) 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

Zirconium(IV) bromide is the inorganic compound with the formula ZrBr4. This colourless solid is the principal precursor to other Zr–Br compounds.

Preparation and properties

ZrBr4 is prepared by the action of bromine on zirconium oxide via a carbothermic reaction:[1]

ZrO2 + 2 C + 2 Br2 → ZrBr4 + 2 CO

Like many related tetrahalides, it is purified by sublimation.

It can also be prepared by treatment of the borohydride complex with hydrogen bromide:[2]

Zr(BH4)4 + 4 HBr → ZrBr4 + 4 H2 + 2 B2H6

Like related tetrabromides of Ti and Hf, ZrBr4 hydrolyzes readily to give the oxybromide, with release of hydrogen bromide.

Structure

No single crystal X-ray study of ZrBr4 has been described. Some reports suggest that it is isostructural with TiCl4 and TiBr4, featuring tetrahedral metal centers.[3] Other studies indicate a polymeric structure.[4] ZrCl4 is polymeric in the solid state, featuring octahedral Zr centers.[5]

References

  1. R. C. Young, Hewitt G. Fletcher, "Anhydrous Zirconium Tetrabromide" Inorganic Syntheses, 1939, vol. 1, pp. 49–51. doi:10.1002/9780470132326.ch18
  2. Calderazzo, Fausto; Pallavicini, Piersandro; Pampaloni, Guido (1990). "Arene derivatives of zirconium(II) and hafnium(II)". Journal of the Chemical Society, Dalton Transactions (6): 1813. doi:10.1039/DT9900001813. 
  3. Berdonosov, S. S.; Lapitskii, A. V. (1963). "Structure of Zr and Hf Tetrabromides". Vestnik Moskovskogo Universiteta, Seriya 2: Khimiya 18: 42–4. "(from abstract): The structure was assumed to be similar to that of SnI4 ... was verified by comparing exptl. and calcd. line intensities, by using Cu K radiation for powder patterns. ... Based on the value of the radius of the I− ion, the lattice parameter and the theoretical sp. gravity of ZrI4 and HfI4 were calcd.". 
  4. Carter, J. C.; Smith, J. A. S. (1974). "Nuclear quadrupole resonance in hafnium and zirconium tetrabromide". Journal of the Chemical Society, Chemical Communications (20): 835–6. doi:10.1039/c39740000835. 
  5. A. F. Wells (1984). Structural Inorganic Chemistry. Oxford: Clarendon Press. ISBN 0-19-855370-6.