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Updated: Nov 25, 2025
Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology
Published on: March 12, 2015
Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions
Conrad A P Goodwin1,2, Marcus J Giansiracusa1, Samuel M Greer2,3,4
1Department of Chemistry, School of Natural Sciences, The University of Manchester, Manchester, UK.
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.
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