One ligand to bind them all: S~C~S2- carbon- and sulfur-based gem-dianion as structuring ligand for iron polymetallic assemblies and the reduction of CO ₂ Sandip Munshi Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier, Toulouse, France 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-electron reduction processes, such as the conversion of N 2 to ammonia, and this of CO 2 into methane and alkenes. The most challenging parameter to imitate is the central carbide ligand, which is believed to maintain the integrity of iron sulfide assembly during catalytic cycles. We propose the use of bis(diphenylphosphinoyl)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. We also evidenced the ability of the mixed- valence di-iron complex {[(μ 2 -SCS) 2 Fe 2 ][B(C 6 F 5 ) 4 ]}to reduce CO 2 , liberating CO and an oxo ligand to make the tetramer. References 1. Chem. Eur. J., 2023. DOI: 10.1002/chem.202302130.2. Chem. Rev.2020, 120 , 5082.3. 2. Proc. Natl. Acad. Sci. U.S.A. 2012, 109 , 19644.4. 3. Science 2011, 334 , 974.5. Chem. Commun. 2012, 48 , 3306.6. 4. Chem. Sci. 2012, 3 , 1680.7. Inorg. Chem. 2010, 49 , 2427.8. Chem. Sci. 2013, 4 , 4042.9. 5. Nat. Commun. 2018, 9 , 3757.
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