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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| Format: | Article |
| Language: | English |
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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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| author | Satoshi Takebayashi Jama Ariai Sergey V. Kartashov Robert R. Fayzullin Tomoko Onoue Ko Mibu Hyung-Been Kang Noriko Ishizu |
| author_facet | Satoshi Takebayashi Jama Ariai Sergey V. Kartashov Robert R. Fayzullin Tomoko Onoue Ko Mibu Hyung-Been Kang Noriko Ishizu |
| author_sort | Satoshi Takebayashi |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-cbd3402817c34018aeb087b73b6961aa |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-cbd3402817c34018aeb087b73b6961aa2025-08-20T03:43:22ZengNature PortfolioNature Communications2041-17232025-07-0116111110.1038/s41467-025-61343-7From 18- to 20-electron ferrocene derivatives via ligand coordinationSatoshi Takebayashi0Jama Ariai1Sergey V. Kartashov2Robert R. Fayzullin3Tomoko Onoue4Ko Mibu5Hyung-Been Kang6Noriko Ishizu7Organometallic Chemistry Group, Okinawa Institute of Science and Technology Graduate UniversityInstitute of Organic Chemistry, Justus Liebig University GiessenArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of SciencesArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of SciencesGraduate School of Engineering, Nagoya Institute of TechnologyGraduate School of Engineering, Nagoya Institute of TechnologyEngineering Section, Okinawa Institute of Science and Technology Graduate UniversityEngineering Section, Okinawa Institute of Science and Technology Graduate UniversityAbstract 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.https://doi.org/10.1038/s41467-025-61343-7 |
| spellingShingle | Satoshi Takebayashi Jama Ariai Sergey V. Kartashov Robert R. Fayzullin Tomoko Onoue Ko Mibu Hyung-Been Kang Noriko Ishizu From 18- to 20-electron ferrocene derivatives via ligand coordination Nature Communications |
| title | From 18- to 20-electron ferrocene derivatives via ligand coordination |
| title_full | From 18- to 20-electron ferrocene derivatives via ligand coordination |
| title_fullStr | From 18- to 20-electron ferrocene derivatives via ligand coordination |
| title_full_unstemmed | From 18- to 20-electron ferrocene derivatives via ligand coordination |
| title_short | From 18- to 20-electron ferrocene derivatives via ligand coordination |
| title_sort | from 18 to 20 electron ferrocene derivatives via ligand coordination |
| url | https://doi.org/10.1038/s41467-025-61343-7 |
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