Titanium tetrabromide

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Titanium tetrabromide
Titanium tetrabromide
Ball-and-stick model of the titanium tetrabromide molecule
Names
IUPAC name
Titanium(IV) bromide
Other names
Titanium tetrabromide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.029.259 Edit this at Wikidata
EC Number
  • 232-185-0
UNII
  • InChI=1S/4BrH.Ti/h4*1H;/q;;;;+4/p-4
    Key: UBZYKBZMAMTNKW-UHFFFAOYSA-J
  • [Ti](Br)(Br)(Br)Br
Properties
TiBr4
Molar mass 367.483 g/mol
Appearance brown crystals
hygroscopic
Density 3.25 g/cm3
Melting point 39 °C (102 °F; 312 K)
Boiling point 230 °C (446 °F; 503 K)
hydrolyses
Solubility in other solvents chlorocarbons, benzene
Structure
cubic, Pa3, Z = 8
Tetrahedral
0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 corrosive
GHS labelling:[1]
GHS05: Corrosive
Danger
H314
P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P363, P405
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
0
1
Flash point Non-flammable
Related compounds
Other anions
 Titanium(IV) chloride
Titanium(IV) fluoride
Titanium(IV) iodide
Related compounds
 Titanium(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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Titanium tetrabromide is the chemical compound with the formula TiBr4. It is the most volatile transition metal bromide. The properties of TiBr4 are an average of TiCl4 and TiI4. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr4 is diamagnetic, reflecting the d0 configuration of the metal centre.[2]

Preparation and structure

This four-coordinated complex adopts a tetrahedral geometry. It can be prepared via several methods: (i) from the elements, (ii) via the reaction of TiO2 with carbon and bromine (see Kroll process), and (iii) by treatment of TiCl4 with HBr.

Reactions

Titanium tetrabromide forms adducts such as TiBr4(THF)2 and [TiBr5]−.[3] With bulky donor ligands, such as 2-methylpyridine (2-Mepy), five-coordinated adducts form. TiBr4(2-MePy) is trigonal bipyramidal with the pyridine in the equatorial plane.[4]

TiBr4 has been used as a Lewis-acid catalyst in organic synthesis.[5]

The tetrabromide and tetrachlorides of titanium react to give a statistical mixture of the mixed tetrahalides, TiBr4−xClx (x = 0-4). The mechanism of this redistribution reaction is uncertain. One proposed pathway invokes the intermediacy of dimers.[6]

Safety

TiBr4 hydrolyzes rapidly, potentially dangerously, to release hydrogen bromide, otherwise known as hydrobromic acid.

References

  1. ^ "Titanium tetrabromide". pubchem.ncbi.nlm.nih.gov. Retrieved 12 December 2021.
  2. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  3. ^ Colin S. Creaser & J. Alan Creighton (1975). "Pentachloro- and pentabromo-titanate(IV) ions". J. Chem. Soc., Dalton Trans. (14): 1402–1405. doi:10.1039/DT9750001402.
  4. ^ Hensen, K.; Lemke, A.; Bolte, M. (2000). "Tetrabromo(2-methylpyridine-N)-titanate(IV)". Acta Crystallographica. C56 (12): e565–e566. Bibcode:2000AcCrC..56E.565H. doi:10.1107/S0108270100015407.
  5. ^ B. Patterson, S. Marumoto & S. D. Rychnovsky (2003). "Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations". Org. Lett. 5 (17): 3163–3166. doi:10.1021/ol035303n. PMID 12917007.
  6. ^ S. P. Webb & M. S. Gordon (1999). "Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br)". J. Am. Chem. Soc. 121 (11): 2552–2560. doi:10.1021/ja983339i.
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