PCET‐Driven Reactivity of Neptunyl(VI) Yields Oxo‐Bridged Np(V) and Np(IV) Species

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

doi:10.1002/chem.202402963

PCET‐Driven Reactivity of Neptunyl(VI) Yields Oxo‐Bridged Np(V) and Np(IV) Species

Journal Article · Mon Dec 02 00:00:00 EST 2024 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202402963· OSTI ID:2574170

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

Two unconventional polynuclear complexes of neptunium (Np) featuring mono-mathematical equation -oxo motifs have been accessed by proton-coupled electron transfer (PCET) reactivity involving the dissolution of neptunyl(VI) diacetate dihydrate (NpO₂(OAc)₂(H₂O)₂ ∙ HOAc) in methanol followed by addition of a pentadentate Schiff-base ligand. One complex is a mixed-valent [Np^V ,Np^IV, Np^V] trimer with two bridging mathematical equation μ₂-oxos and the other is a [Np^V, Np^V] dimer featuring a single mathematical equation μ₂-oxo. In both complexes the outer Np centers are capped with terminal oxo ligands. Spectroscopic and spectrokinetic studies aimed at elucidating mechanistic details of complex formation in this system show that intermediate multinuclear [Np^VO₂ (OAc)]ⁿ species form prior to metal chelation by the ligand; electrolysis experiments demonstrate that production of Np(V) gives rise to asynchronous proton transfer that does not occur otherwise (in the Np(VI) state) as well as condensation with loss of H₂O and formation of the polynuclear complexes. We attribute the oxo-deficient nature of these products, with respect to conventional actinyl ([AnO₂]^m+) species, to the reduction/condensation reaction sequence of PCET.

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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); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

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

OSTI ID:: 2574170

Alternate ID(s):: OSTI ID: 2530684

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 6 Vol. 31; ISSN 0947-6539; ISSN 1521-3765

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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