From Square-Planar [ICl ] to Novel Chloroiodates(III)? A Systematic Experimental and Theoretical Investigation of Their Ionic Liquids.

A systematic investigation on the existence of chloroiodates formed by reaction of Cl with I Cl , apart from the well-known [ICl ] , namely [I Cl ] and [I Cl ] , was undertaken by employing theoretical as well as experimental methods. The thermodynamic stability in terms of the complexation enthalpies and Gibbs energies, and also the decomposition of the iodine(III) polyinterhalogen anions through dichlorine elimination to form iodine (I) compounds, was studied by means of DFT and ab initio quantum-chemical calculations up to an extrapolated CCSD(T)/A'QZ level. On the experimental side, mixtures of [HMIM]Cl ([HMIM] =1-hexyl-3-methylimidazolium), [BMP]Cl ([BMP] =1-butyl-1-methylpyrrolidinium chloride) and [NEt ]Cl with 0.