Puneet Varma (Editor)

Titanium tetraiodide

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Appearance
  
red-brown crystals

Molar mass
  
555.485 g/mol

Boiling point
  
377 °C

Coordination geometry
  
tetrahedral

Formula
  
TiI4

Density
  
4.3 g/cm³

Melting point
  
150 °C

Titanium tetraiodide httpsuploadwikimediaorgwikipediacommonsthu

Related compounds
  
titanium tetrachloride, titanium tetrabromide, titanium(III) iodide, I2, Ta2I10

Solubility in other solvents
  
soluble in CH2Cl2; CHCl3; CS2

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.

Contents

Physical properties

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.

Production

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.

Reactions

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.

References

Titanium tetraiodide Wikipedia