From 18- to 20-electron ferrocene derivatives via ligand coordination
Abstract 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 coordi...
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| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61343-7 |
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| Summary: | Abstract 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. |
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| ISSN: | 2041-1723 |