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Tuning the structure, reactivity and magnetic communication of nitride-bridged uranium complexes with the ancillary
Chad T Palumbo1, Luciano Barluzzi1, Rosario Scopelliti1
1Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland .
Abstract:
Molecular uranium nitride complexes were prepared to relate their small molecule reactivity to the nature of the U[double bond, length as m-dash]N[double bond, length as m-dash]U bonding imposed by the supporting ligand. The U4+-U4+ nitride complexes, [NBu4][{(( BuO)3SiO)3U}2(μ-N)], [NBu, and [NBu4][((Me3Si)2N)3U}2(μ-N)], 2, were synthesised by reacting NBu4N3 with the U3+ complexes, [U(OSi(O Bu)3)2(μ-OSi(O Bu)3)]2 and [U(N(SiMe3)2)3], respectively. Oxidation of 2 with AgBPh4 gave the U4+-U5+ analogue, [((Me3Si)2N)3U}2(μ-N)], 4. The previously reported methylene-bridged U4+-U4+ nitride [Na(dme)3][((Me3Si)2)2U(μ-N)(μ-κ2-C,N-CH2SiMe2NSiMe3)U(N(SiMe3)2)2] (dme = 1,2-dimethoxyethane), [Na(dme), provided a versatile precursor for the synthesis of the mixed-ligand U4+-U4+ nitride complex, [Na(dme)3][((Me3Si)2N)3U(μ-N)U(N(SiMe3)2)(OSi(O Bu)3)], 5. The reactivity of the 1-5 complexes was assessed with CO2, CO, and H2. Complex [NBu displays similar reactivity to the previously reported heterobimetallic complex, [Cs{(( BuO)3SiO)3U}2(μ-N)], [Cs]-1, whereas the amide complexes 2 and 4 are unreactive with these substrates. The mixed-ligand complexes 3 and 5 react with CO and CO2 but not H2. The nitride complexes [NBu, 2, 4, and 5 along with their small molecule activation products were structurally characterized. Magnetic data measured for the all-siloxide complexes [NBu and [Cs]-1 show uncoupled uranium centers, while strong antiferromagnetic coupling was found in complexes containing amide ligands, namely 2 and 5 (with maxima in the χ versus T plot of 90 K and 55 K). Computational analysis indicates that the U(μ-N) bond order decreases with the introduction of oxygen-based ligands effectively increasing the nucleophilicity of the bridging nitride.
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