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Titanium(IV) iodide

Titanium tetraiodide
Titanium tetraiodide
Titanium tetraiodide
Names
IUPAC name
Titanium(IV) iodide
Other names
Titanium tetraiodide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.868
EC Number 231-754-0
PubChem CID
Properties
TiI4
Molar mass 555.485 g/mol
Appearance red-brown crystals
Density 4.3 g/cm3
Melting point 150 °C (302 °F; 423 K)
Boiling point 377 °C (711 °F; 650 K)
hydrolysis
Solubility in other solvents soluble in CH2Cl2
CHCl3
CS2
Structure
cubic (a = 12.21 Å)
tetrahedral
0 D
Hazards
Main hazards violent hydrolysis
corrosive
R-phrases (outdated) 34-37
S-phrases (outdated) 26-36/37/39-45
Related compounds
Related compounds
titanium tetrachloride, titanium tetrabromide,
titanium(III) iodide,
I2, Ta2I10
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N  (what is YesYN ?)
Infobox references

Titanium tetraiodide is an inorganic compound with the formula TiI4. It is a black volatile solid, first reported by Rudolph Weber in 1863. It is an intermediate in the Van Arkel process for the purification of titanium.

TiI4 is a rare molecular binary metal iodide, consisting of isolated molecules of tetrahedral Ti(IV) centers. The Ti-I distances are 261 pm. Reflecting its molecular character, TiI4 can be distilled without decomposition at one atmosphere; this property is the basis of its use in the Van Arkel process. The difference in melting point between TiCl4 (m.p. -24 °C) and TiI4 (m.p. 150 °C) is comparable to the difference between the melting points of CCl4 (m.p. -23 °C) and CI4 (m.p. 168 °C), reflecting the stronger intermolecular van der Waals bonding in the iodides.

Two polymorphs of TiI4 exist, one of which is highly soluble in organic solvents. In the less soluble cubic form, the Ti-I distances are 261 pm.

Three methods are well known: 1) From the elements, typically using a tube furnace at 425 °C:

This reaction can be reversed to produce highly pure films of Ti metal.

2) Exchange reaction from titanium tetrachloride and HI.

3) Oxide-iodide exchange from aluminium iodide.

Like TiCl4 and TiBr4, TiI4 forms adducts with Lewis bases, and it can also be reduced. When the reduction is conducted in the presence of Ti metal, one obtains polymeric Ti(III) and Ti(II) derivatives such as CsTi2I7 and the chain CsTiI3, respectively. As a solution in CH2Cl2, TiI4 exhibits some reactivity toward alkenes and alkynes resulting in organoiodine derivatives.


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