A review will be given of our research in the field of iodine chemistry including the following topics. Using IF5 as a solvent for halogen fluoride ions, the IF6+, IF6-, I2F11- and I3F16- ions were synthesized and characterized. Subsequently, the IF2-, IF4-, IF4+, and IF4O- ions were prepared. The most interesting species was the IF52- anion which has an unprecedented pentagonal-planar structure. The long-standing problems of the fluxionality of IF7 and the steric activity of the free valence electron pair in the halogen hexafluoride anions were solved. At the limits of coordination and oxidation, the IF5O2-, IF5O22- and IF6O-, the first examples of pentagonal-bipyramidal AX5E2, AX5EO, AX5O2, and AX5YZ species, were prepared, and a novel method for the stepwise replacement of two fluorines in iodine fluorides by an oxygen was developed. With I(ClO4)3 and I(ClO4)4-, the first examples of highly explosive iodine perchlorates were discovered, and fluorocarbon perchlorates were prepared by the reaction of fluorocarbon iodides with halogen perchlorates. Similarly, chlorine fluorosulfate and perfluoroisopropyl iodide yield i-C3F7I(SO3F)2, a compound with an iodonium cation and an iodite anion. Iodine fluorosulfate, ISO3F, can also be added across olefinic double bonds producing iodoperfluorocarbon fluorosulfates. Further examples of the broad scope of this work are the syntheses of FOIF4O, ClOIF4O, HOIF4O, and tetrafluoroperiodates, and the study of the polymorphism in tetramethylammonium periodate. Recently, the long missing I2O7 was synthesized and the potential of I2O6 as an agent for the defeat of weapons of mass destruction was demonstrated. Most of these compounds are not only of academic interest but have many applications as High Energy Density Materials, explosives, propellants, and chemical lasers.

Award Address (ACS Award for Creative Research and Applications of Iodine Chemistry sponsored by SQM S.A.). Fifty years of Iodine research

249th National Meeting (2015)

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