my-server
← Wiki Redirected from Zirconium triiodide

Zirconium(III) iodide

Zirconium(III) iodide is an inorganic compound with the formula ZrI<sub>3</sub>.

Preparation

Like other group 4 trihalides, zirconium(III) iodide can be prepared from zirconium(IV) iodide by high-temperature reduction with zirconium metal, although incomplete reaction and contamination of the product with excess metal often occurs.

3 ZrI<sub>4</sub> + Zr → 4 ZrI<sub>3</sub>

An alternative is to crystallise zirconium(III) iodide from a solution of zirconium(III) in aluminium triiodide. The solution is prepared by reducing a eutectic solution of ZrI<sub>4</sub> in liquid AlI<sub>3</sub> at a temperature of 280–300 °C with metallic zirconium or aluminium.

Structure and bonding

Zirconium(III) iodide has a lower magnetic moment than is expected for the d<sup>1</sup> metal ion Zr<sup>3+</sup>, indicating non-negligible Zr–Zr bonding.

The crystal structure of zirconium(III) iodide is based on hexagonal close packing of iodide ions with one third of the octahedral interstices occupied by Zr<sup>3+</sup> ions. The structure consists of parallel chains of face-sharing {ZrI<sub>6</sub>} octahedra with unequally spaced metal atoms. The Zr–Zr separation alternates between 3.17 Å and 3.51 Å.

ZrCl<sub>3</sub>, ZrBr<sub>3</sub> and ZrI<sub>3</sub> adopt structures very similar to the β-TiCl<sub>3</sub> structure. In all three ZrX<sub>3</sub> there is some elongation of the octahedra along the metal-metal axis, partly due to metal-metal repulsion, but the elongation is most pronounced in the chloride, moderate in the bromide and negligible in the iodide.

References