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• W3110987002 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 Cpttt ligands (where Cpttt 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. Unlike ferrocene and its cationic counterpart ferrocenium, the ferrocene monoanion is an unusual species that has been observed through low-temperature electrochemical studies. Now, a family of isostructural 3d metallocenates has been isolated that consists of a manganocene, a cobaltocene and a high-spin ferrocene anion stabilized by cyclopentadienyl ligands bearing bulky aliphatic groups." @default.
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• W3110987002 date "2020-12-14" @default.
• W3110987002 modified "2023-10-17" @default.
• W3110987002 title "Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions" @default.
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• W3110987002 doi "https://doi.org/10.1038/s41557-020-00595-w" @default.
• W3110987002 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/7610420" @default.
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