Since the first reports and structural characterisation of ferrocene in the 1950s, metallocenes [M(Cp)2] (M=metal, Cp=cyclopentadienyl, C5H5) have become a workhorse of organometallic chemistry. The vast majority of metallocenes and derivatized metallocenes [M(CpR)2], where the CpR 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(CpR)2]+. Here we present an overview of metallocene anions and their derivatives, [M(CpR)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.
The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the...
The Front Cover shows a depiction of a classical metallocene anion, with a red metal atom in a formal +I oxidation state sandwiched by two cyclopentadienyl rings. The central image is flanked by a range of d‐transition metal(I) ions, together with a selection of derivatized five‐membered carbocyclic rings, representing the d‐block metallocene anions that have been structurally authenticated to date. The review covers the chemistry of metallocene anions and their derivatives, focusing on d‐block examples, and provides a historical overview from their detection as intermediates in low‐temperature electrochemical studies to the most recent examples of isolated complexes. The cover was designed by Corentin Magnoux. More information can be found in the Review by C. Magnoux and D. P. Mills.
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