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The reaction of laser‐ablated iridium atoms with dinitrogen molecules and nitrogen atoms yield several neutral and ionic iridium dinitrogen complexes such as Ir(N2), Ir(N2)+, Ir(N2)2, Ir(N2)2−, IrNNIr, as well as the nitrido complexes IrN, Ir(N)2 and IrIrN. These reaction products were deposited in solid neon, argon and nitrogen matrices and characterized by their infrared spectra. Assignments of vibrational bands are supported by ab initio and first principle calculations as well as 14/15N isotope substitution experiments. The structural and electronic properties of the new dinitrogen and nitrido iridium complexes are discussed. While the formation of the elusive dinitrido complex Ir(N)2 was observed in a subsequent reaction of IrN with N atoms within the cryogenic solid matrices, the threefold coordinated iridium trinitride Ir(N)3 could not be observed so far. [ABSTRACT FROM AUTHOR]

Front Cover: A Cornucopia of Iridium Nitrogen Compounds Produced from Laser-Ablated Iridium Atoms and Dinitrogen (Chem. Eur. J. 33/2020) Keywords: density functional calculations; high oxidation states; matrix isolation; nitrogen fixation; transition metals EN density functional calculations high oxidation states matrix isolation nitrogen fixation transition metals 7331 7331 1 06/12/20 20200610 NES 200610 B Iridium, the "rainbow" element, b is the element with the highest attainable formal oxidation state of +IX. This reaction leads to a cornucopia of iridium nitrogen compounds identified by FTIR spectroscopy under cryogenic conditions. [Extracted from the article]