title: Investigation of Uranium Tris(imido) Complexes: Synthesis, Characterization, and Reduction Chemistry of [U(NDIPP)3(thf)3].
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 U(V) 5f (1) centers, with no antiferromagnetic coupling present. Characterization of these complexes was accomplished using single-crystal X-ray diffraction, variable-temperature (1)H NMR spectroscopy, as well as IR and UV/Vis absorption spectroscopic studies.
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA).
authors.forename: Nickolas H
authors.initials: NH
authors.lastname: Anderson
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104 (USA).
authors.forename: Haolin
authors.initials: H
authors.lastname: Yin
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA).
authors.forename: John J
authors.initials: JJ
authors.lastname: Kiernicki
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA).
authors.forename: Phillip E
authors.initials: PE
authors.lastname: Fanwick
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104 (USA).
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA). sbart@purdue.edu.
authors.forename: Suzanne C
authors.initials: SC
authors.lastname: Bart
keywords: imido; magnetic properties; multiple bonds; reduction; uranium