1. Unusual Actinyl Complexes with a Redox-Active N,S-Donor Ligand.
- Author
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Su J, Gong Y, Batista ER, Lucena AF, Maria L, Marçalo J, Van Stipdonk MJ, Berden G, Martens J, Oomens J, Gibson JK, and Yang P
- Abstract
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, C
5 H4 NS, acts as a monoanion in [UVI O2 (C5 H4 NS- )]+ but as a neutral radical with unpaired electrons localized on the sulfur atom in [NpV O2 (C5 H4 NS• )]+ and [PuV O2 (C5 H4 NS• )]+ , 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 C5 H4 NS- ligand and the cooperativity between An-N and An-S bonds that provides additional stability for the transuranic elements.- Published
- 2023
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