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Ammonium Pertechnetate in Mixtures of Trifluoromethanesulfonic Acid and Trifluoromethanesulfonic Anhydride

Markus Zegke, Dennis Grödler, Maximilian Roca Jungfer, Alexander Haseloer, Meike Kreuter, Jörg‐M. Neudörfl, Thomas Sittel, Christopher M. James, Jörg Rothe, Marcus Altmaier, Axel Klein, Martin Breugst, Ulrich Abram, Erik Strub, Mathias S. Wickleder

2021Angewandte Chemie International Edition27 citationsDOIOpen Access PDF

Abstract

Abstract Ammonium pertechnetate reacts in mixtures of trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid under final formation of ammonium pentakis(trifluoromethanesulfonato)oxidotechnetate(V), (NH 4 ) 2 [TcO(OTf) 5 ]. The reaction proceeds only at exact concentrations and under the exclusion of air and moisture via pertechnetyl trifluoromethanesulfonate, [TcO 3 (OTf)], and intermediate Tc VI species. 99 Tc nuclear magnetic resonance (NMR) has been used to study the Tc VII compound and electron paramagnetic resonance (EPR), 99 Tc NMR and X‐ray absorption near‐edge structure (XANES) experiments indicate the presence of the reduced technetium species. In moist air, (NH 4 ) 2 [TcO(OTf) 5 ] slowly hydrolyses under formation of the tetrameric oxidotechnetate(V) (NH 4 ) 4 [{TcO(TcO 4 ) 4 } 4 ] ⋅10 H 2 O. Single‐crystal X‐ray crystallography was used to determine the solid‐state structures. Additionally, UV/Vis absorption and IR spectra as well as quantum chemical calculations confirm the identity of the species.

Topics & Concepts

ChemistryTrifluoromethanesulfonateAmmoniumAbsorption spectroscopyElectron paramagnetic resonanceXANESNMR spectra databaseInorganic chemistryChemical shiftAbsorption (acoustics)Spectral linePhysical chemistryOrganic chemistryNuclear magnetic resonanceCatalysisMaterials scienceComposite materialPhysicsQuantum mechanicsAstronomyRadioactive element chemistry and processingChemical Synthesis and CharacterizationInorganic and Organometallic Chemistry
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