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A tetrahedral neptunium(V) complex
Journal article   Peer reviewed

A tetrahedral neptunium(V) complex

Julie E Niklas, Kaitlyn S Otte, Chad M Studvick, Sabyasachi Roy Chowdhury, Bess Vlaisavljevich, John Bacsa, Florian Kleemiss, Ivan A Popov and Henry S La Pierre
Nature chemistry, Vol.16(9), pp.1490-1495
09/2024
DOI: 10.1038/s41557-024-01529-6
PMID: 38710831

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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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