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Uranium-Ligand Multiple Bonding


QEf8An improved understanding of bonding and redox behavior of uranium has the potential to impact on a number of areas aside from nuclear energy and waste remediation, such as establishing the usefulness of its complexes for organic/inorganic transformations. We recently demonstrated that the enhanced reactivity of a new U(III) complex, [U(κ6-{(tBu2ArO)2Me2-cyclam})I], as reductant allowed to prepare a series of new uranium species in different oxidation states anchored on bis(phenolate) cyclam ligand, including uranium-nitrogen multiple bond complexes. In an effort to synthesize uranium-oxo compounds supported by this ligand, reactions of the complexes [UIII6-{(tBu2ArO)2Me2-cyclam})I] and [UIVI6-{(tBu2ArO)2Me-cyclam})]I with oxygen-atom-transfer reagents (e.g. pyridine-N-oxide, NaNO2) were tested. A new dimeric uranyl complex [(UVIO2)2(μ-{(tBu2ArO)2Me-cyclam)2(thf)]2 could be obtained from oxidation of the U(IV) compound with NaNO2. The cleavage of the nitrite anion by the uranium(IV) cation efficiently replaced the uranium-iodide bond by terminal uranium-oxo bonds.


Contact person: Leonor Maria