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DOE OSTI · 2340721

Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution 13 C NMR Spectroscopy

Ordoñez, Osvaldo·Yu, Xiaojuan·Wu, Guang·Autschbach, Jochen·Hayton, Trevor W.
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Abstract

Reaction of [UO 2 Cl 2 (THF) 2 ] 2 with in situ generated LiFmes (FmesH = 1,3,5-(CF 3 ) 3 C 6 H 3 ) in Et 2 O resulted in the formation of the uranyl aryl complexes [Li(THF) 3 ][UO 2 (Fmes) 3 ] ([Li(THF) 3 ][1]) and [Li(Et 2 O) 3 (THF)][UO 2 (Fmes) 3 ] ([Li(Et 2 O) 3 (THF)][1]) in good to moderate yields after crystallization from hexanes and Et 2 O, respectively. Both complexes were characterized by X-ray crystallography and NMR spectroscopy. DFT calculations reveal that the C ispo resonance in [1] – exhibits a deshielding of 51 ppm from spin–orbit coupling effects originating at uranium, which indicates an appreciable covalency in the U–C bonding interaction.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYDFT calculationsUraniumcationsligandsresonance structures

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Ordoñez, Osvaldo, Yu, Xiaojuan, Wu, Guang, Autschbach, Jochen, Hayton, Trevor W.. 2023-10-03. Quantifying Actinide–Carbon Bond Covalency in a Uranyl–Aryl Complex Utilizing Solution 13 C NMR Spectroscopy. https://doi.org/10.1021/acs.inorgchem.3c02440

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