Schaub Stefan, Miska Andreas, Becker Jonathan, Zahn Stefan, Mollenhauer Doreen, Sakshath Sadashivaiah, Schünemann Volker, Schindler Siegfried
Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 17, 35392, Gießen, Germany.
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstraße 2, 04103, Leipzig, Germany.
Angew Chem Int Ed Engl. 2018 May 4;57(19):5355-5358. doi: 10.1002/anie.201800475. Epub 2018 Apr 11.
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 (H O)(tmc)Fe=O) could be prepared. This complex is important in regard to a better understanding of the reactivity of Fe oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s and a quadrupole splitting ΔE =1.38 mm s , confirming the high-valent Fe state. DFT calculations were performed and led to an assignment of triplet spin multiplicity. Crystallographic characterization of (H O)(tmc)Fe=O) as well as of starting materials (tmc)Fe(CH CN) and [(tmc)Fe(OTf)]OTf together with previous results strongly suggest that (H O)(tmc)Fe=O) was formed similar to the oxido-hydroxido tautomerism analogous to heme systems.
已使用臭氧作为氧化剂合成了具有大环配体1,4,8,11 - 四甲基 - 1,4,8,11 - 四氮杂环十四烷（tmc）的铁（IV）氧化合物[(tmc)Fe=O(OTf)]OTf。通过向该化合物中加水，可以制备配合物(H₂O)(tmc)Fe=O。该配合物对于更好地理解铁氧化合物的反应性很重要。使用固体化合物进行的穆斯堡尔测量显示，异构体位移δ = 0.19 mm s⁻¹，四极分裂ΔE = 1.38 mm s⁻¹，证实了高价铁状态。进行了密度泛函理论（DFT）计算，并得出了三重态自旋多重性的归属。(H₂O)(tmc)Fe=O以及起始原料(tmc)Fe(CH₃CN)和[(tmc)Fe(OTf)]OTf的晶体学表征与先前的结果一起强烈表明，(H₂O)(tmc)Fe=O的形成类似于与血红素系统类似的氧化 - 羟基互变异构。
