Titanium tetrabromide


Titanium tetrabromide

Chembox new
Name = Titanium tetrabromide
ImageFile = TiBr4.png ImageName = Titanium tetrabromide
ImageFile1 = Titanium-tetrabromide-3D-balls.png ImageName1 = Ball-and-stick model of the titanium tetrabromide molecule
IUPACName = Titanium tetrabromide
OtherNames = Titanium(IV) bromide
Section1 = Chembox Identifiers
CASNo = 7789-68-6
RTECS =

Section2 = Chembox Properties
Formula = TiBr4
MolarMass = 367.48 g/mol
Appearance = brown crystals, hygroscopic
Density = 3.25 g/mL at 25 °C, solid
Solubility = decomposition
Solvent = other solvents
SolubleOther = chlorocarbons, benzene
MeltingPt = 38-40 °C
BoilingPt = 230 °C

Section3 = Chembox Structure
Coordination = Tetrahedral
Dipole = 0 D

Section7 = Chembox Hazards
ExternalMSDS =
MainHazards = corrosive
FlashPt = nonflammable
RPhrases = 14-34
SPhrases = 26-36/37/39-45

Section8 = Chembox Related
OtherAnions = TiCl4
TiI4
OtherCations = VCl4
OtherCpds = TiCl3
VBr3

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. [Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.]

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

TiBr4 forms adducts such as TiBr4(THF)2 and [TiBr5] -. [cite journal | journal = J. Chem. Soc., Dalton Trans. | year = 1975 | pages = 1402–1405 | doi = 10.1039/DT9750001402 | title =Pentachloro- and pentabromo-titanate(IV) ions | author = Colin S. Creaser and J. Alan Creighton] 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. [cite journal | author = Hensen, K.; Lemke, A.; Bolte, M. | title = Tetrabromo(2-methylpyridine-N)-titanate(IV) | journal = Acta Crystallographica | year = 2000 | volume = C56 | pages = e565 - e566 | doi = 10.1107/S0108270100015407]

TiBr4 has been used as a Lewis-acid catalyst in organic synthesis. [cite journal | author = B. Patterson, S. Marumoto and S. D. Rychnovsky | title = Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations | year = 2003 | journal = Org. Lett. | volume = 5 | issue = 17 | pages = 3163–3166 | doi = 10.1021/ol035303n]

TiBr4 reacts rapidly with TiCl4 to give a statistical mixture of the tetrahalides, TiBr4-xClx (x = 0-4). The mechanism of this exchange is a matter of some dispute; a reasonable pathway involves the intermediacy of dimers. [cite journal | author = S. P. Webb and M. S. Gordon | title = Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br) | year = 1999 | journal = J. Am. Chem. Soc. | volume = 121 | issue = 11 | pages = 2552–2560 | doi = 10.1021/ja983339i]

afety

TiBr4 hydrolyzes rapidly, potentially dangerously, to release hydrogen bromide.

References


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