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A tetrahedral neptunium(V) complex.

Authors :: Niklas JE
Otte KS
Studvick CM
Roy Chowdhury S
Vlaisavljevich B
Bacsa J
Kleemiss F
Popov IA
La Pierre HS
Source :: Nature chemistry [Nat Chem] 2024 Sep; Vol. 16 (9), pp. 1490-1495. Date of Electronic Publication: 2024 May 06.
Publication Year :: 2024
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 ([Np <superscript>5+</superscript> (NPC) <subscript>4</subscript> ][B(ArF <subscript>5</subscript> ) <subscript>4</subscript> ], 1-Np) (NPC = [NP <superscript>t</superscript> Bu(pyrr) <subscript>2</subscript> ] <superscript>-</superscript> ; <superscript>t</superscript> Bu = C(CH <subscript>3</subscript> ) <subscript>3</subscript> ; pyrr = pyrrolidinyl (N(C <subscript>2</subscript> H <subscript>4</subscript> ) <subscript>2</subscript> ); B(ArF <subscript>5</subscript> ) <subscript>4</subscript> = 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.<br /> (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)