From 18- to 20-electron ferrocene derivatives via ligand coordination.
basic_science · Level V
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- Record sourced from PubMed, PMID 40624059.
- Also identified by DOI 10.1038/s41467-025-61343-7 and PMC identifier 12234732.
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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 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.