Synthesis of an Iron(IV) Aqua–Oxido Complex Using Ozone as an Oxidant |
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| Authors: | Stefan Schaub Andreas Miska Dr Jonathan Becker Dr Stefan Zahn Prof?Dr Doreen Mollenhauer Dr Sadashivaiah Sakshath Prof?Dr Volker Schünemann Prof?Dr Siegfried Schindler |
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| Institution: | 1. Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universit?t Gie?en, Heinrich-Buff-Ring 17, 35392 Gie?en, Germany;2. Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universit?t Leipzig, Linnéstra?e 2, 04103 Leipzig, Germany;3. Institut für Physikalische Chemie, Justus-Liebig-Universit?t Gie?en, Heinrich-Buff-Ring 17, 35392 Gie?en, Germany;4. Fachbereich Physik, Technische Universit?t Kaiserslautern, Schr?dinger Stra?e 46, 67663 Kaiserslautern, Germany |
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| Abstract: | The iron(IV) oxido complex (tmc)Fe=O(OTf)]OTf with the macrocyclic ligand 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclo‐tetradecane (tmc) has been synthesized using ozone as an oxidant. By adding water to this compound the complex (H2O)(tmc)Fe=O)](OTf)2 could be prepared. This complex is important in regard to a better understanding of the reactivity of FeIV oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s?1 and a quadrupole splitting ΔEQ=1.38 mm s?1, confirming the high‐valent FeIV state. DFT calculations were performed and led to an assignment of triplet spin multiplicity. Crystallographic characterization of (H2O)(tmc)Fe=O)](OTf)2 as well as of starting materials (tmc)Fe(CH3CN)](OTf)2 and (tmc)Fe(OTf)]OTf together with previous results strongly suggest that (H2O)(tmc)Fe=O)](OTf)2 was formed similar to the oxido–hydroxido tautomerism analogous to heme systems. |
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| Keywords: | bioinorganic chemistry Mö ssbauer spectroscopy non-heme iron complexes ozone tetramethylcyclam |
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