| Autor: |
Meiqi Li, Hao Li, Cancan Ling, Huan Shang, Hui Wang, Shengxi Zhao, Chuan Liang, Chengliang Mao, Furong Guo, Biao Zhou, Zhihui Ai, Lizhi Zhang |
| Předmět: |
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| Zdroj: |
Proceedings of the National Academy of Sciences of the United States of America; 9/19/2023, Vol. 120 Issue 38, p1-43, 50p |
| Abstrakt: |
High-valent iron-oxo species (FeIV=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 FeIV=O (=FeIV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2 -) as the oxidant, which possesses an impressive =FeIV=O selectivity of 99%. =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 =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 =FeIV=O. With methyl phenyl sulfoxide (PMS16O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18O transfer from Cl18O2 - to PMS16O18O mediated by =FeIV=18O. We then showcase the versatility of =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 =FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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