One Ligand to Bind them All: S~C~S2− Carbon‐ and Sulfur‐Based Gem‐Dianion as Structuring Ligand for Iron Polymetallic Assemblies.

Numerous synthetic models of the FeMo‐co cluster of nitrogenases have been proposed to find the simplest structure with relevant reactivity. Indeed, such structures are able to perform multi‐electrons reduction processes, such as the conversion of N2 to ammonia, and of CO2 into methane and alkenes. The most challenging parameter to imitate is indeed the central carbide ligand, which is believed to maintain the integrity of iron sulfide assembly during the course of catalytic cycles. The study proposes the use of bis(diphenylthiophosphinoyl)methanediide (SCS)2− as an ideal platform for the synthesis of bi‐ and tetra‐metallic iron complexes, in which the iron‐carbon interaction is maintained upon structural diversification and redox state changes. [ABSTRACT FROM AUTHOR]