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

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Abstract

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
Volume13
Issue number3
DOIs
Publication statusPublished - 14 Dec 2020

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