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Updated: Jul 12, 2026
Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron
Published on: August 12, 2019
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.
Abstract:
We present compelling evidence for the first Fe- and Co-ozonido complexes: [(D12-TMC)FeIII(O3)(OTf)](BArF), [(D12-TMC)FeIII(O3)(I)](BArF), and {[(D12-TMC)CoIII(F)]2(O3)}(BArF)2 from the reactions of complexes [(D12-TMC)FeII(X)]BArF and [(D12-TMC)CoII(X)]BArF (X = OTf, F, I) with ozone in 2-Me-THF/THF solutions using ultraviolet-visible spectroscopic and cryospray mass spectrometric techniques at cryogenic temperatures as low as -155°C (118 K). Further reactivity studies suggest the subsequent formation of Fe- and Co-oxido complexes [(D12-TMC)FeIV(O)(OTf)]BArF, [(D12-TMC)CoIV(O)(OTf)]BArF, and [(D12-TMC)CoIV(O)(F)]BArF. Density functional theory computations with the ωB97X-3c three-component method and the ωB97X-D4 hybrid functional corroborate our spectroscopic results. Further key results of our studies entail the synthesis of several hitherto unreported Fe and Co complexes, including complexes with strongly (F) and moderately stabilizing (OTf) anions without extraneous coordinated solvent molecules. The D12-TMC ligand proves to be effective for preventing methyl group hydroxylation as observed, for example, in the case of [(TMCO)CoIII(H2O)](OTf)2. With ozonide [N(CH3)4]O3, we instead obtained crystals of [(D12-TMC-propyl-O)CoIII(OTf)]BArF from [(D12-TMC)CoII(OTf)]BArF. The generation of these transient Fe- and Co-complexes demonstrates that temperatures below values attainable by typical stopped-flow setups in conjunction with "ligand hardening" provide a promising strategy for studies of reactive complexes.
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