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Identification of an iridium-containing compound with a formal oxidation state of IX.

Title	Identification of an iridium-containing compound with a formal oxidation state of IX.
Authors	Guanjun Wang, Mingfei Zhou, James T. Goettel, Gary J. Schrobilgen, Jing Su, Jun Li, Tobias Schlöder, Sebastian Riedel
Magazine	Nature
Date	10/22/2014
DOI	10.1038/nature13795
Introduction	The concept of formal oxidation states is a fundamental classification in chemistry and within the periodic table. There is considerable interest among chemists in the synthesis and characterization of compounds containing elements with uncommon oxidation states. Currently, the highest experimentally verified formal oxidation state for any chemical element is VIII, exemplified by xenon compounds such as XeO4 and XeO3F2, and well-established species like RuO4 and OsO4. Iridium, possessing nine valence electrons, is theoretically considered to have the highest potential for oxidation beyond the VIII state. Previous matrix-isolation experiments successfully characterised the IrO4 molecule as an isolated species in rare-gas matrices, where iridium exhibits a 5d(1) valence electron configuration and a formal oxidation state of VIII. Theoretical studies suggested that the removal of the remaining d electron from IrO4 would yield the iridium tetroxide cation ([IrO4]+), predicted to be stable with iridium in a formal oxidation state of IX. While the formation of [IrO4]+ species has been discussed, prior experimental observations lacked structural confirmation. This work details the formation of [IrO4]+ and its identification through infrared photodissociation spectroscopy. Advanced quantum-chemical calculations support that the iridium tetroxide cation, adopting a Td-symmetrical structure with a d(0) electron configuration, represents the most stable configuration among all potential [IrO4]+ isomers.
Quote	Guanjun Wang, Mingfei Zhou and James T. Goettel et al. Identification of an iridium-containing compound with a formal oxidation state of IX. 2014. DOI: 10.1038/nature13795
Element	Iridium (Ir) , Oxygen (O)
Industry	Research & Laboratory

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