Electroanalytical characterization of Np(VI)/Np(V) redox in a pentadentate ligand environment and stabilization of [NpVO2]+ by hydrogen bonding

Mikeska, Emily R.; Curry, T. Davis; Wilson, Richard E.; Blakemore, James D.

doi:10.1039/d4dt02557a

Electroanalytical characterization of Np(VI)/Np(V) redox in a pentadentate ligand environment and stabilization of [Np^VO₂]⁺ by hydrogen bonding

Journal Article · Mon Oct 28 00:00:00 EDT 2024 · Dalton Transactions

DOI:https://doi.org/10.1039/d4dt02557a· OSTI ID:2479976

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University of Kansas, Lawrence, KS (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
University of Kansas, Lawrence, KS (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

The redox chemistry of the actinyl cations (AnO₂ⁿ⁺) heavily influences their reactivity and speciation in solution, but the redox properties of the actinyls in non-aqueous media have received far less attention than they deserve. Here, the non-aqueous electrochemistry of a chemically reversible Np(VI)/Np(V) redox manifold is reported in both protic (CH₃OH) and aprotic (CH₃CN) organic media. Using a neutral Np(VI) complex supported by a chelating and strongly donating pentadentate ligand that was fully characterized in prior work, a clean Np(VI)/Np(V) redox couple was found to be accessible under ambient conditions. Coupled electrochemical and spectroscopic studies, as well as simulations of cyclic voltammetry data, confirm the 1e− nature of this couple and establish it to be chemically reversible and nearly electrochemically reversible as well. Bulk electrolysis of a solution of the neutral Np(VI) complex facilitated isolation of the corresponding anionic and monomeric Np(V) species. Data from X-ray diffraction analysis as well as optical and vibrational spectroscopies provide strong evidence in support of metal-centered reduction and the Np(V) oxidation state, findings that are in accord with the measured reduction potentials. Distinctive hydrogen bonding interactions between the terminal (yl) oxo groups and water molecules appear to stabilize the isolated Np(V) species in the solid state, providing insight into the features that afford the uncommon chemically reversible redox encountered in this system.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; SC0014664; SC0019169

OSTI ID:: 2479976

Alternate ID(s):: OSTI ID: 2583971

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 48 Vol. 53; ISSN 1477-9226; ISSN 1477-9234

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Electroanalytical characterization of Np(VI)/Np(V) redox in a pentadentate ligand environment and stabilization of [Np^VO₂]⁺ by hydrogen bonding