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Identification of a Two-Coordinate Iron(I)-Oxalate Complex
Martin Mayer1, Nina Vankova2, Ferdinand Stolz3
1Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstr. 2, 04103, Leipzig, Germany.
Abstract:
Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron-oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [FeIII (C2 O4 )2 ]- , [FeII (C2 O4 )CO2 ]- , and [FeI (C2 O4 )]- were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.
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