Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
Authors:
- 10 February 2012
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (10) , 4931-4940
Abstract
Reaction of UCl4 with 5 equiv of Li(N═CtBuPh) generates the homoleptic U(IV) ketimide complex [Li(THF)2][U(N═CtBuPh)5] (1) in 71% yield. Similarly, reaction of UCl4 with 5 equiv of Li(N═CtBu2) affords [Li(THF)][U(N═CtBu2)5] (2) in 67% yield. Oxidation of 2 with 0.5 equiv of I2 results in the formation of the neutral U(V) complex U(N═CtBu2)5 (3). In contrast, oxidation of 1 with 0.5 equiv of I2, followed by addition of 1 equiv of Li(N═CtBuPh), generates the octahedral U(V) ketimide complex [Li][U(N═CtBuPh)6] (4) in 68% yield. Complex 4 can be further oxidized to the U(VI) ketimide complex U(N═CtBuPh)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.Keywords
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