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First Evidence for Ozonido-TMC Complexes of Iron and Cobalt
Stefan Schaub1, Dennis Gerbig2, Raffael C Wende2
1Institute of Inorganic Chemistry, Justus Liebig University, Giessen, Germany.
Angewandte Chemie (International Ed. in English)
|July 9, 2026
Summary
Researchers synthesized novel iron (Fe) and cobalt (Co) ozonido complexes at extremely low temperatures. These findings advance the study of reactive metal-oxygen species using specialized ligands and cryogenic conditions.
Area of Science:
- Inorganic Chemistry: Synthesis and characterization of novel metal-ozonido and metal-oxido complexes.
- Organometallic Chemistry: Investigation of iron and cobalt complexes with unique ligands and reactive oxygen species.
- Physical Chemistry: Application of cryogenic temperatures and advanced spectroscopic techniques for studying transient species.
Background:
- Ozonido complexes of iron and cobalt are highly reactive and challenging to isolate and study.
- Understanding the reactivity of these transient species is crucial for catalysis and bioinorganic chemistry.
- Previous studies were limited by the instability of ozonido intermediates at higher temperatures.
Purpose of the Study:
- To synthesize and characterize the first iron (Fe) and cobalt (Co) ozonido complexes.
- To investigate the reactivity of these complexes, leading to the formation of oxido species.
- To explore the utility of cryogenic temperatures and specialized ligands for stabilizing reactive intermediates.
Main Methods:
- Reaction of Fe(II) and Co(II) precursors with ozone at cryogenic temperatures (-155°C).
- Characterization using ultraviolet-visible spectroscopy and cryospray mass spectrometry.
- Density functional theory (DFT) computations using ωB97X-3c and ωB97X-D4 functionals.
Main Results:
- Successful synthesis and spectroscopic evidence for the first Fe- and Co-ozonido complexes.
- Observation of subsequent formation of Fe- and Co-oxido complexes.
- DFT calculations corroborated the experimental spectroscopic findings.
- Synthesis of novel Fe and Co complexes with stabilizing anions (OTf, F) and a unique ligand (D12-TMC) that prevents side reactions like methyl group hydroxylation.
Conclusions:
- The combination of cryogenic temperatures and ligand design enables the isolation and study of transient Fe- and Co-ozonido complexes.
- This strategy opens new avenues for investigating reactive metal-oxygen species.
- The developed Fe and Co complexes serve as valuable models for understanding oxidation reactions.
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