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<p>The 18-electron rule is a fundamental rule in coordination chemistry on which several revolutionary discoveries in catalysis and materials science are founded. This rule has classes of exceptions; however, it is widely taught and accepted that diamagnetic 18-electron complexes do not coordinate to a ligand to form a 20-electron complex even as a reaction intermediate. Here, based on tunable ligand design, we report the formation of 20-electron ferrocene derivatives through reversible nitrogen coordination to 18-electron analogs. Through theoretical studies, we have elucidated key features that enabled this coordination chemistry and how the nitrogen coordination shifts the metal−ligand bonding characters. These 20-electron ferrocene derivatives exhibit reversible Fe<sup>II</sup>/Fe<sup>III</sup>/Fe<sup>IV</sup> redox chemistry under previously unattainable, mild conditions. This work highlights the previously unknown coordination chemistry of diamagnetic 18-electron complexes, which underlies the foundation for future innovations in a range of synthetic chemistry.</p>

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From 18- to 20-electron ferrocene derivatives via ligand coordination

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年7月7日

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  • Satoshi Takebayashi,
  • Jama Ariai,
  • Sergey V. Kartashov,
  • Robert R. Fayzullin,
  • Tomoko Onoue,
  • Ko Mibu,
  • Hyung-Been Kang,
  • Noriko Ishizu

摘要

The 18-electron rule is a fundamental rule in coordination chemistry on which several revolutionary discoveries in catalysis and materials science are founded. This rule has classes of exceptions; however, it is widely taught and accepted that diamagnetic 18-electron complexes do not coordinate to a ligand to form a 20-electron complex even as a reaction intermediate. Here, based on tunable ligand design, we report the formation of 20-electron ferrocene derivatives through reversible nitrogen coordination to 18-electron analogs. Through theoretical studies, we have elucidated key features that enabled this coordination chemistry and how the nitrogen coordination shifts the metal−ligand bonding characters. These 20-electron ferrocene derivatives exhibit reversible FeII/FeIII/FeIV redox chemistry under previously unattainable, mild conditions. This work highlights the previously unknown coordination chemistry of diamagnetic 18-electron complexes, which underlies the foundation for future innovations in a range of synthetic chemistry.