Cyclopentadienyl ring activation in organometallic chemistry and catalysis.

The cyclopentadienyl (Cp) ligand is a cornerstone of modern organometallic chemistry. Since the discovery of ferrocene, the Cp ligand and its various derivatives have become foundational motifs in catalysis, medicine and materials science. Although largely considered an ancillary ligand for altering the stereoelectronic properties of transition metal centres, there is mounting evidence that the core Cp ring structure also serves as a reservoir for reactive protons (H + ), hydrides (H - ) or radical hydrogen (H • ) atoms. This Review chronicles the field of Cp ring activation, highlighting the pivotal role that Cp ligands can have in electrocatalytic H 2 production, N 2 reduction, hydride transfer reactions and proton-coupled electron transfer.