Unusual Actinyl Complexes with a Redox-Active N,S-Donor Ligand

Understanding the fundamental chemistry of soft N,S-donor ligands with actinides across the series is critical for separation science toward sustainable nuclear energy. This task is particularly challenging when the ligands are redox active. We herein report a series of actinyl complexes with a N,S-donor redox-active ligand that stabilizes different oxidation states across the actinide series. These complexes are isolated and characterized in the gas phase, along with high-level electronic structure studies. The redox-active N,S-donor ligand in the products, C₅H₄NS, acts as a monoanion in [U^VIO₂(C₅H₄NS^-)]⁺ but as a neutral radical with unpaired electrons localized on the sulfur atom in [Np^VO₂(C₅H₄NS^•)]⁺ and [Pu^VO₂(C₅H₄NS^•)]⁺, resulting in different oxidation states for uranium and transuranic elements. This is rationalized by considering the relative energy levels of actinyl(VI) 5f orbitals and S 3p lone pair orbitals of the C₅H₄NS^- ligand and the cooperativity between An-N and An-S bonds that provides additional stability for the transuranic elements.