Humus State of the Rostov Agglomeration Soils

Skripnikov, Pavel N.; Gorbov, S. N.; Безуглова, О. С.

doi:10.18522/801300097

Cited by 1 publication

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“…The authors have cited additional references within the Supporting Information. [5,[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Complete experimental and methodological details, spectroscopic data (NMR, UV-Vis, IR), selected crystallographic tables, details of theoretical calculations, and calculated cartesian coordinates; (PDF)…”

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confidence: 99%

Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes

Otte

Niklas

Studvick

et al. 2023

Preprint

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The study of the redox chemistry of mid-actinides (U – Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non-aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC = [N=PtBu(pyrr)2]−; pyrr = pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium (1-M, 2-M, M = Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M4+/3+ (M = Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U5+/4+, U6+/5+, and to an unprecedented, well-behaved Np5+/4+ redox couple. The differences in the chemical redox properties of the U vs. Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.

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