CeF4 Complexes in Organic Solvents

Abstract

The first complexes of cerium tetrafluoride in solutions have been studied by ¹⁹F NMR and IR spectroscopy. The temperature dependence of the ¹⁹F NMR spectra has been explored, and conclusion has been made that dynamic equilibrium between the molecular adduct and singly charged ionic forms, including geometric isomers, exists in solution. The statistical probability for the formation of [CeF₄(dmso)₄] stereoisomers of square antiprism configuration has been calculated, and their assignment to possible stereoisomers have been made on the basis of relative intensities of the ¹⁹F NMR signals. Quantum-chemical calculations of the structure of one of the possible isomers have been performed for the [CeF₄(dmso)₄] molecular adduct, [CeF₃(dmso)₅]⁺ cation, and [CeF₅(dmso)₃]^– anion to show their thermodynamic stability.