Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions

Conrad Goodwin, Marcus Giansiracusa, Samuel Greer, Hannah Nicholas, Peter Evans, Michele Vonci, Stephen Hill, Nicholas Chilton, David Mills

Research output: Contribution to journalArticlepeer-review

23 Downloads (Pure)


The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry. Although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low-temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3d metallocenates, which consist of anionic complexes of a metal centre (manganese, iron or cobalt) sandwiched between two bulky Cp ttt ligands (where Cp ttt is {1,2,4-C 5H 2 tBu 3}). These thermally and air-sensitive complexes decompose rapidly above −30 °C; however, we were able to characterize all metallocenates by a wide range of physical techniques and ab initio calculations. These data have allowed us to map the electronic structures of this metallocenate family, including an unexpected high-spin S = 3/2 ground state for the 19e derivatized ferrocene anion. [Figure not available: see fulltext.]

Original languageEnglish
Article number0
Pages (from-to)243-248
Number of pages6
JournalNature Chemistry
Issue number3
Publication statusPublished - 14 Dec 2020


Dive into the research topics of 'Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions'. Together they form a unique fingerprint.

Cite this