Preparation and properties of bis(acetonitrile)iodine(I) hexafluoromolybdate(V) and hexafluorouranate(V)

Abstract

Elemental iodine is oxidized by molybdenum or uranium hexafluoride in acetonitrile at ambient temperature to give bis(acetonitrile) iodine(I) hexafluoromolybdate(V) or hexafluorouranate(V). The solids' vibrational spectra are consistent with linear co-ordination of MeCN to I⁺. Co-ordinated MeCN is readily displaced by pyridine (py) to give an [l(py)₂]⁺ salt. In MeCN solution the solvated I⁺ decomposes to give l₂ as one product, it iodinates benzene and its derivatives, and oxidizes the solvated copper(I) cation, NO, and thallium metal to give the solvated copper(II) cation, NO⁺, and a mixture of solvated cations of Tl^I and Tl^III respectively. The solvated thallium(III) cation oxidizes iodine ion in MeCN at room temperature giving I₂ or solvated I⁺ depending on the concentration ratio. Oxidation states of solvated thallium cations are conveniently identified by ²⁰⁵TI n.m.r. spectroscopy.