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Reactions of a Uranium(III) Complex with N-Heterocycles to Form Diuranium(IV) Ketimides
Conrad A P Goodwin1,2, Michael Godsall1, Shuhan Zhang1,2
1Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Abstract:
The chemistry of the classical uranium(III) complex [U(N″)3] (N″ = {N(SiMe3)2}-) is well-developed; however, there have been surprisingly few studies of its reactivity toward N-heterocycles. Here, we report the separate reactions of [U(N″)3] with pyrazine, 4-azido-pyridine, and the methylene transfer agent N-(9,10-dihydro-9,10-epiminoanthracen-11-yl)methanimine (C14H10N2CH2) to give the respective diuranium(IV) products [{U(N″)3}2(μ-NC4H4N-1κN,2κN')] (1), [{U(N″)3}2(μ-NC5H4N-1κN,2κN')] (2), and [{U(N″)3}2(μ-NC14H10N-1κN,2κN')] (3). The solid-state structures of complexes 2 and 3 respectively revealed bent U-N═C angles of 167.6(5) and 155.3(4)°, short U-N bond lengths of 2.070(5) and 2.104(4) Å, and diagnostic C═Nketimide distances of 1.297(7) and 1.364(7) Å. A combination of structural, spectroscopic, magnetic, and quantum-chemical calculations was required to confidently assign U(IV) ions exclusively in complexes 1-3 and to prove that 2 and 3 are ketimides rather than iminyls or nitrenes. Together, this study underscores the need for comprehensive analysis for the correct interpretation of the electronic structures of actinide complexes.
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