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

Autor: Shiels D; Department of Chemistry, University of Rochester Rochester NY 14627 USA dshiels@ur.rochester.edu matson@chem.rochester.edu., Brennessel WW; Department of Chemistry, University of Rochester Rochester NY 14627 USA dshiels@ur.rochester.edu matson@chem.rochester.edu., Crawley MR; Department of Chemistry, University at Buffalo, The State University of New York Buffalo NY 14620 USA., Matson EM; Department of Chemistry, University of Rochester Rochester NY 14627 USA dshiels@ur.rochester.edu matson@chem.rochester.edu.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2024 Jun 17; Vol. 15 (28), pp. 11072-11083. Date of Electronic Publication: 2024 Jun 17 (Print Publication: 2024).
DOI: 10.1039/d4sc02644f
Abstrakt: The synthesis and characterization of a series of (TBA) 2 [M{Mo 5 O 13 (OMe) 4 NO} 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 {Mo 5 } 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{Mo 5 O 13 (OMe) 4 NO} 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.
Competing Interests: The authors declare no competing financial interest.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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