2020
DOI: 10.1038/s41557-020-00595-w
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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 3 d metallocenates which consist of anionic complexes of a… Show more

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Cited by 49 publications
(54 citation statements)
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“…The metallocene family is composed of central transition metal atoms and organic cyclopentadienyl groups (Goodwin et al, 2021). Among of them, ferrocene, which is aromatic and contains easily replaced sites, shows a high redox activity in the field of electrochemistry (Benecke et al, 2020).…”
Section: Metal-organic Hybrid Electrocatalystsmentioning
confidence: 99%
“…The metallocene family is composed of central transition metal atoms and organic cyclopentadienyl groups (Goodwin et al, 2021). Among of them, ferrocene, which is aromatic and contains easily replaced sites, shows a high redox activity in the field of electrochemistry (Benecke et al, 2020).…”
Section: Metal-organic Hybrid Electrocatalystsmentioning
confidence: 99%
“… Current vs. potential plots using ferrocene +/0 as reference electrode recorded at −50 °C for 9 – 11 (reprinted with permission from ref. [10g]). …”
Section: Figurementioning
confidence: 99%
“…This observation is in agreement with the spectroscopic measurements and theoretical calculations.F urthermore,i solation of 8 and the room-temperature stable bis-phospholyl [K(2.2.2cryptand)][Fe(PC 4 Me 4 ) 2 ]( 15) [12] leads to the inference that the presence of an appropriate heteroatom in the ring can stabilize unusual oxidation states of the first-row transition metals.E xtensive studies on dicationic and monoanionic ferrocene ions throw light on how controlling the substituents on the C 5 ring as well as choosing appropriate redox environments can afford previously believed to be difficult synthetic targets. [5,10,12,13] Making these anions stable at room temperature will be the next step in this area of research, which does not seem to be too far away. Molecular orbital ordering and occupationn umbers obtained from ab initio calculations along with the symmetry of the orbitals for ferrocenate (B) and cobaltocenate (D) anions.…”
mentioning
confidence: 99%
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