AI Article Synopsis
- Two unique polynuclear complexes of neptunium (Np) with mono-μ2-oxo structures were created through a reaction involving the neptunyl(VI) compound dissolving in methanol and the addition of a Schiff-base ligand.
- One complex forms a trimer with mixed-valent Np centers and two bridging μ2-oxos, while the other is a dimer with two Np centers and one bridging μ2-oxo.
- Studies show that an intermediate multinuclear species forms before the ligand binds to the metal, and the oxo-deficient nature of the final products results from the electron transfer and condensation reactions involved in the complex formation.
Article Abstract
Two unconventional polynuclear complexes of neptunium (Np) featuring mono- -oxo motifs have been accessed by proton-coupled electron transfer (PCET) reactivity involving the dissolution of neptunyl(VI) diacetate dihydrate ( HOAc) in methanol followed by addition of a pentadentate Schiff-base ligand. One complex is a mixed-valent [Np ,Np ,Np ] trimer with two bridging -oxos and the other is a [Np ,Np ] dimer featuring a single -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 (OAc)] 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 and formation of the polynuclear complexes. We attribute the oxo-deficient nature of these products, with respect to conventional actinyl ([AnO ] ) species, to the reduction/condensation reaction sequence of PCET.
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| http://dx.doi.org/10.1002/chem.202402963 | DOI Listing |
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