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 Fe^IV oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s⁻¹ and a quadrupole splitting ΔE_Q=1.38 mm s⁻¹, confirming the high‐valent Fe^IV 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.

中文翻译：

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臭氧作为氧化剂合成铁（IV）水-氧配合物

已合成具有大环配体1,4,8,11-四甲基-1,4,8,11-四氮杂环-十四烷（tmc）的铁（IV）氧化络合物[（tmc）Fe = O（OTf）] OTf使用臭氧作为氧化剂。通过将水添加到该化合物中，可以制备络合物[（H ₂ O）（tmc）Fe = O）]（OTf）₂。对于更好地理解Fe ^IV氧化物配合物的反应性而言，该配合物很重要。使用固体化合物进行的Mössbauer测量显示出δ = 0.19 mm s ^-1的异构体位移和四极分裂ΔE _Q = 1.38 mm s ^-1，证实了高价Fe ^IV状态。进行了DFT计算，并得出了三重态自旋多重性的赋值。[（H ₂ O）（tmc）Fe = O）]（OTf）₂以及起始原料[（tmc）Fe（CH ₃ CN）]（OTf）₂和[（tmc）Fe（OTf）的晶体学表征）] OTf和先前的结果强烈表明，[（H ₂ O）（tmc）Fe = O）]（OTf）_2的形成类似于类似于血红素系统的氧化-羟基互变异构。