A tetrahedral neptunium(V) complex.

Autor: Niklas JE; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA., Otte KS; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA., Studvick CM; Department of Chemistry, The University of Akron, Akron, OH, USA., Roy Chowdhury S; Department of Chemistry, University of South Dakota, Vermillion, SD, USA., Vlaisavljevich B; Department of Chemistry, University of South Dakota, Vermillion, SD, USA., Bacsa J; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA., Kleemiss F; Institut für Anorganische Chemie, RWTH Aachen University, Aachen, Germany., Popov IA; Department of Chemistry, The University of Akron, Akron, OH, USA. ipopov@uakron.edu., La Pierre HS; School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA. hsl@gatech.edu.; Nuclear and Radiological Engineering and Medical Physics Program, School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA. hsl@gatech.edu.; Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, USA. hsl@gatech.edu.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2024 Sep; Vol. 16 (9), pp. 1490-1495. Date of Electronic Publication: 2024 May 06.
DOI: 10.1038/s41557-024-01529-6
Abstrakt: 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 5+ (NPC) 4 ][B(ArF 5 ) 4 ], 1-Np) (NPC = [NP t Bu(pyrr) 2 ] - ; t Bu = C(CH 3 ) 3 ; pyrr = pyrrolidinyl (N(C 2 H 4 ) 2 ); B(ArF 5 ) 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.
(© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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