Scholarlink

<p>Surface high-valent iron-oxo species (≡Fe<sup>IV</sup>=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<sup>IV</sup> = O (PA-≡Fe<sup>IV</sup> = O) on pyrite using chlorite as the oxidant, where the in-situ generated ClO<sub>2</sub> can transform a planar Fe-S bond to Fe-Cl by oxidizing and subsequently substituting planar sulfur atoms. Different from planar symmetric surface Fe<sup>IV</sup> = O (PS-≡Fe<sup>IV</sup> = O) with electron localization around axial Fe = O, PA-≡Fe<sup>IV</sup> = 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<sup>IV</sup> = O, realizing more efficient oxygen atom transfer oxidation of methane, methyl phenyl sulfide, triphenylphosphonate and styrene than PS-≡Fe<sup>IV</sup> = O. This study offers a facile approach for the synthesis of planar asymmetric surface Fe<sup>IV</sup> = O, and also underscores the importance of planar coordination environment of high-valent metal-oxo species in the oxygen atom transfer reactions.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

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

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年7月1日

查看全文
  • Wengao Lian,
  • Hengyue Xu,
  • Xingyue Zou,
  • Jie Dai,
  • Meiqi Li,
  • Cancan Ling,
  • Yunhao Shen,
  • Hao Li,
  • Yancai Yao,
  • Lizhi Zhang

摘要

Surface high-valent iron-oxo species (≡FeIV=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 FeIV = O (PA-≡FeIV = O) on pyrite using chlorite as the oxidant, where the in-situ generated ClO2 can transform a planar Fe-S bond to Fe-Cl by oxidizing and subsequently substituting planar sulfur atoms. Different from planar symmetric surface FeIV = O (PS-≡FeIV = O) with electron localization around axial Fe = O, PA-≡FeIV = 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-≡FeIV = O, realizing more efficient oxygen atom transfer oxidation of methane, methyl phenyl sulfide, triphenylphosphonate and styrene than PS-≡FeIV = O. This study offers a facile approach for the synthesis of planar asymmetric surface FeIV = O, and also underscores the importance of planar coordination environment of high-valent metal-oxo species in the oxygen atom transfer reactions.