Planar asymmetric surface FeIV = O synthesis with pyrite and chlorite for efficient oxygen atom transfer reactions

• Published in: Nature communications Vol. 16; no. 1; pp. 5989 - 8
• Main Authors: Lian, Wengao, Xu, Hengyue, Zou, Xingyue, Dai, Jie, Li, Meiqi, Ling, Cancan, Shen, Yunhao, Li, Hao, Yao, Yancai, Zhang, Lizhi
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.07.2025; Nature Publishing Group; Nature Portfolio
• Subjects: 140/133; 140/58; 147/135; 147/137; 639/638/169/896; 639/638/224/685; 639/638/77/885; 639/638/77/887; Asymmetry; Chlorine; Coordination; Electron transfer; Electrons; Fourier transforms; Humanities and Social Sciences; Iron; Ligands; Localization; multidisciplinary; Oxidants; Oxidation; Oxidizing agents; Oxygen; Polystyrene resins; Pyrite; Reagents; Science; Science (multidisciplinary); Small mammals; Styrene; Sulfur; Synthesis
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-025-60919-7

Surface high-valent iron-oxo species (≡Fe IV =O) are reliable and green oxygen atom transfer reagents, but the ability is seriously inhibited by the maximal orbital overlap of axial Fe = O double bond in a symmetric planar coordination environment. Herein, we report the synthesis of planar asymmetric surface Fe IV  = O (PA-≡Fe IV  = O) on pyrite using chlorite as the oxidant, where the in-situ generated ClO 2 can transform a planar Fe-S bond to Fe-Cl by oxidizing and subsequently substituting planar sulfur atoms. Different from planar symmetric surface Fe IV  = O (PS-≡Fe IV  = O) with electron localization around axial Fe = O, PA-≡Fe IV  = O delocalizes electrons among Fe, axial oxo moiety and its planar ligands owing to the stronger electron-withdrawing capacity of Cl, which effectively weakens the orbital overlap of axial Fe = O bonding and thus facilitates the rapid electron transfer from the substrates to the unoccupied antibonding orbital of PA-≡Fe IV  = O, realizing more efficient oxygen atom transfer oxidation of methane, methyl phenyl sulfide, triphenylphosphonate and styrene than PS-≡Fe IV  = O. This study offers a facile approach for the synthesis of planar asymmetric surface Fe IV  = O, and also underscores the importance of planar coordination environment of high-valent metal-oxo species in the oxygen atom transfer reactions. Surface high-valent iron-oxo species (≡Fe⁴⁺=O) are effective and environmentally friendly reagents for oxygen atom transfer. Here, the authors create a planar, asymmetric ≡Fe⁴⁺=O with a Fe–Cl₁S₃ structure using pyrite and chlorite, which enhances electron delocalization and weakens the Fe=O bond to improve reaction efficiency.