Investigation of Uranium Tris(imido) Complexes: Synthesis,Characterization, and Reduction Chemistry of [U(NDIPP)3(thf)3] |
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| Authors: | Nickolas H. Anderson Haolin Yin John J. Kiernicki Dr. Phillip E. Fanwick Prof. Eric J. Schelter Prof. Suzanne C. Bart |
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| Affiliation: | 1. H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA);2. P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104 (USA) |
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| Abstract: | Addition of KC8 to trivalent [UI3(thf)4] in the presence of three equivalents of 2,6‐diisopropylphenylazide (N3DIPP) results in the formation of the hexavalent uranium tris(imido) complex [U(NDIPP)3(thf)3] ( 1 ) through a facile, single‐step synthesis. The X‐ray crystal structure shows an octahedral complex that adopts a facial orientation of the imido substituents. This structural trend is maintained during the single‐electron reduction of 1 to form dimeric [U(NDIPP)3{K(Et2O)}]2 ( 2 ). Variable‐temperature/field magnetization studies of 2 show two independent UV 5f 1 centers, with no antiferromagnetic coupling present. Characterization of these complexes was accomplished using single‐crystal X‐ray diffraction, variable‐temperature 1H NMR spectroscopy, as well as IR and UV/Vis absorption spectroscopic studies. |
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| Keywords: | imido magnetic properties multiple bonds reduction uranium |
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