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. 2024 Sep;16(9):1490-1495.
doi: 10.1038/s41557-024-01529-6. Epub 2024 May 6.

A tetrahedral neptunium(V) complex

Julie E Niklas #  1 , Kaitlyn S Otte #  1 , Chad M Studvick  2 , Sabyasachi Roy Chowdhury  3 , Bess Vlaisavljevich  3 , John Bacsa  1 , Florian Kleemiss  4 , Ivan A Popov  5 , Henry S La Pierre  6   7   8
Affiliations

A tetrahedral neptunium(V) complex

Julie E Niklas et al. Nat Chem. 2024 Sep.

Abstract

Neptunium is an actinide element sourced from anthropogenic production, and, unlike naturally abundant uranium, its coordination chemistry is not well developed in all accessible oxidation states. High-valent neptunium generally requires stabilization from at least one metal-ligand multiple bond, and departing from this structural motif poses a considerable challenge. Here we report a tetrahedral molecular neptunium(V) complex ([Np5+(NPC)4][B(ArF5)4], 1-Np) (NPC = [NPtBu(pyrr)2]-; tBu = C(CH3)3; pyrr = pyrrolidinyl (N(C2H4)2); B(ArF5)4 = tetrakis(2,3,4,5,6-pentafluourophenyl)borate). Single-crystal X-ray diffraction, solution-state spectroscopy and density functional theory studies of 1-Np and the product of its proton-coupled electron transfer (PCET) reaction, 2-Np, demonstrate the unique bonding that stabilizes this reactive ion and establishes the thermochemical and kinetic parameters of PCET in a condensed-phase transuranic complex. The isolation of this four-coordinate, neptunium(V) complex reveals a fundamental reaction pathway in transuranic chemistry.

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