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

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-C₅H₂ ^tBu₃}). 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.

SUBMITTER: Goodwin CAP

PROVIDER: S-EPMC7610420 | biostudies-literature |

REPOSITORIES: biostudies-literature

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