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Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation of a stable U(v) sandwich complex.

ABSTRACT: The synthesis and characterization of a series of (TBA)2[M{Mo5O13(OMe)4NO}2] (M = Zr, Hf, Th, and U) sandwich complexes is reported. A preformed lacunary, Lindqvist-type, polyoxomolybdate-alkoxide cluster provides access to first examples of actinide-polyoxomolybdate sandwich complexes isolated under non-aqueous conditions. Incorporation of metal(iv) cations into this framework was found to "switch on" reversible redox chemistry at the {Mo5} ligands, with the Zr and Hf containing complexes accepting up to two electrons, while the Th and U derivates accommodate as many as four additional electrons. The enhancement of the redox properties of the cluster upon actinide incorporation is an exciting observation, presenting actinide "doping" as a novel approach for accessing functional redox-active materials. Oxidation of the uranium containing sandwich complex (TBA)2[U{Mo5O13(OMe)4NO}2], chemically or electrochemically, allows access to the U(v) centered species, which was characterized both spectroscopically and by single crystal X-ray diffraction. This represents the first example of a U(v)-polyoxometalate sandwich complex to be isolated and structurally characterized.

SUBMITTER: Shiels D 

PROVIDER: S-EPMC11253122 | biostudies-literature | 2024 Jul

REPOSITORIES: biostudies-literature

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Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation of a stable U(v) sandwich complex.

Shiels Dominic D   Brennessel William W WW   Crawley Matthew R MR   Matson Ellen M EM  

Chemical science 20240617 28

The synthesis and characterization of a series of (TBA)<sub>2</sub>[M{Mo<sub>5</sub>O<sub>13</sub>(OMe)<sub>4</sub>NO}<sub>2</sub>] (M = Zr, Hf, Th, and U) sandwich complexes is reported. A preformed lacunary, Lindqvist-type, polyoxomolybdate-alkoxide cluster provides access to first examples of actinide-polyoxomolybdate sandwich complexes isolated under non-aqueous conditions. Incorporation of metal(iv) cations into this framework was found to "switch on" reversible redox chemistry at the {Mo<s  ...[more]

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