Probing the 5f orbital contribution to the bonding in a U(V) ketimide complex |
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Authors: | Seaman Lani A Wu Guang Edelstein Norman Lukens Wayne W Magnani Nicola Hayton Trevor W |
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Institution: | Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States. |
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Abstract: | Reaction of UCl(4) with 5 equiv of Li(N═C(t)BuPh) generates the homoleptic U(IV) ketimide complex Li(THF)(2)]U(N═C(t)BuPh)(5)] (1) in 71% yield. Similarly, reaction of UCl(4) with 5 equiv of Li(N═C(t)Bu(2)) affords Li(THF)]U(N═C(t)Bu(2))(5)] (2) in 67% yield. Oxidation of 2 with 0.5 equiv of I(2) results in the formation of the neutral U(V) complex U(N═C(t)Bu(2))(5) (3). In contrast, oxidation of 1 with 0.5 equiv of I(2), followed by addition of 1 equiv of Li(N═C(t)BuPh), generates the octahedral U(V) ketimide complex Li]U(N═C(t)BuPh)(6)] (4) in 68% yield. Complex 4 can be further oxidized to the U(VI) ketimide complex U(N═C(t)BuPh)(6) (5). Complexes 1-5 were characterized by X-ray crystallography, while SQUID magnetometry, EPR spectroscopy, and UV-vis-NIR spectroscopy measurements were also preformed on complex 4. Using this data, the crystal field splitting parameters of the f orbitals were determined, allowing us to estimate the amount of f orbital participation in the bonding of 4. |
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