Highly selective synthesis of surface FeIV=O with nanoscale zero- valent iron and chlorite for efficient oxygen transfer reactions

作者：Li, Meiqi; Li, Hao^*; Ling, Cancan; Shang, Huan; Wang, Hui; Zhao, Shengxi; Liang, Chuan; Mao, Chengliang; Guo, Furong; Zhou, Biao; Ai, Zhihui^*; Zhang, Lizhi^*

来源：PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2023, 120(38): e2304562120.

DOI：10.1073/pnas.2304562120

• Surface high-valent iron-oxo species
• oxygen atom transfer
• nanoscale zero-valent iron
• chlorite
• selective synthesis

High-valent iron-oxo species (Fe-IV=O) has been a long-sought- after oxygen transfer reagent in biological and catalytic chemistry but suffers from a giant challenge in its gentle and selective synthesis. Herein, we propose a new strategy to synthesize surface Fe-IV=O (equivalent to Fe-IV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2-) as the oxidant, which possesses an impressive equivalent to FeIV=O selectivity of 99%. equivalent to FeIV=O can be energetically formed from the ferrous (FeII) sites on nZVI through heterolytic Cl-O bond dissociation of ClO2- via a synergistic effect between electron-donating surface equivalent to FeII and proximal electron-withdrawing H2O, where H2O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO2- thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of =FeII toward the final formation of equivalent to Fe-IV=O. With methyl phenyl sulfoxide ((PMSO)-O-16) as the probe molecule, the isotopic labeling experiment manifests an exclusive O-18 transfer from (ClO2-)-O-18 to (PMSOO)-O-16-O-18 mediated by equivalent to FeIV=O-18. We then showcase the versatility of equivalent to FeIV=O as the oxygen transfer reagent in activating the C-H bond of methane for methanol production and facilitating selective triphenylphosphine oxide synthesis with triphenylphosphine. We believe that this new equivalent to FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value- added chemical synthesis.

• 单位
  上海交通大学