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Metallocene Anions: From Electrochemical Curiosities to Isolable Complexes
Author(s) -
Magnoux Corentin,
Mills David P.
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202101063
Subject(s) - chemistry , metallocene , cyclopentadienyl complex , ferrocene , heteroatom , ring (chemistry) , metal , electrochemistry , organometallic chemistry , oxidation state , group 2 organometallic chemistry , polymer chemistry , stereochemistry , inorganic chemistry , crystallography , medicinal chemistry , molecule , organic chemistry , crystal structure , catalysis , electrode , polymer , polymerization
Since the first reports and structural characterisation of ferrocene in the 1950s, metallocenes [M(Cp) 2 ] (M=metal, Cp=cyclopentadienyl, C 5 H 5 ) have become a workhorse of organometallic chemistry. The vast majority of metallocenes and derivatized metallocenes [M(Cp R ) 2 ], where the Cp R ring bears alternative substituents or incorporates heteroatoms in the ring itself, contain metal centres in a formal +II oxidation state, or +III for metallocenium cations, [M(Cp R ) 2 ] + . Here we present an overview of metallocene anions and their derivatives, [M(Cp R ) 2 ] − , where metal centres formally exhibit +I oxidation states. We focus on d‐block examples, from their origins as unstable intermediates in low temperature electrochemical studies to more recent examples of isolated complexes.