Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides
نویسندگان
چکیده
Uranium nitride complexes are attractive targets for chemists as molecular models the bonding, reactivity, and magnetic properties of next-generation nuclear fuels, but these molecules uncommon can be difficult to isolate due their high reactivity. Here, we describe synthesis three new multinuclear uranium complexes, [U(BCMA)2]2(μ-N)(μ-κ1:κ1-BCMA) (7), [(U(BIMA)2)2(μ-N)(μ-NiPr)(K2(μ-η3:η3-CH2CHNiPr)]2 (8), [U(BIMA)2]2(μ-N)(μ-κ1:κ1-BIMA) (9) (BCMA = N,N-bis(cyclohexyl)methylamidinate, BIMA N,N-bis(iso-propyl)methylamidinate), from U(III) U(IV) amidinate precursors. By varying ligand substituents azide source, were able influence composition size complexes. 15N isotopic labeling experiments confirmed bridging moieties in 7–9 formed via two-electron reduction azide. The tetra-uranium cluster 8 was isolated 99% yield reductive cleavage ligands; this unusual molecule contains nitrogen-based ligands with formal 1–, 2–, 3– charges. Additionally, chemical oxidation precursor U(N3)(BCMA)3 yielded cationic U(V) species [U(N3)(BCMA)3][OTf]. Magnetic susceptibility measurements a state centers nitride-bridged provided comparison behavior structurally related U(III)-U(IV)-U(V) series U(BCMA)3, U(N3)(BCMA)3, At 240 K, moments decreased increasing state, i.e., > U(V); trend follows decreasing number 5f valence electrons along series.
منابع مشابه
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ژورنال
عنوان ژورنال: Inorganic Chemistry
سال: 2021
ISSN: ['0020-1669', '1520-510X']
DOI: https://doi.org/10.1021/acs.inorgchem.1c00471