title: Synthesis and Reduction of Uranium(V) Imido Complexes with Redox-Active Substituents.
abstract: Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes UV[=NC(2-naph)Ph2][N(SiMe3)2]3(2), UV[=NC(2-naph)3][N(SiMe3)2]3(3), and UV[=N(2-naph)][N(SiMe3)2]3(4), and their properties were compared with UV[=NCPh3][N(SiMe3)2]3(1). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible UV/VI, UIV/V, and naphthalene0/naphthalene-1couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[UIV[=NC(2-naph)Ph2][N(SiMe3)2]3] (2-K), K[UIV[=NC(2-naph)3][N(SiMe3)2]3] (3-K), and K[UIV[=N(2-naph)][N(SiMe3)2]3] (4-K). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand-based, which opens the possibility of accomplishing multi-electron redox chemistry by using a tailored multiply-bonded ligand.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, PA, 19104, USA.
authors.forename: Kimberly C
authors.initials: KC
authors.lastname: Mullane
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, PA, 19104, USA.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, PA, 19104, USA.
authors.forename: Eric J
authors.identifier: http://orcid.org/0000-0002-8143-6206
authors.initials: EJ
authors.lastname: Schelter
keywords: electrochemistry; electronic structure; imido; redox chemistry; uranium