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

Satoshi Takebayashi (), Jama Ariai, Sergey V. Kartashov, Robert R. Fayzullin (), Tomoko Onoue, Ko Mibu, Hyung-Been Kang and Noriko Ishizu
Additional contact information
Satoshi Takebayashi: Okinawa Institute of Science and Technology Graduate University
Jama Ariai: Justus Liebig University Giessen
Sergey V. Kartashov: Russian Academy of Sciences
Robert R. Fayzullin: Russian Academy of Sciences
Tomoko Onoue: Nagoya Institute of Technology
Ko Mibu: Nagoya Institute of Technology
Hyung-Been Kang: Okinawa Institute of Science and Technology Graduate University
Noriko Ishizu: Okinawa Institute of Science and Technology Graduate University

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: 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.

Date: 2025
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-025-61343-7 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-61343-7

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-025-61343-7

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().