title: Harnessing redox activity for the formation of uranium tris(imido) compounds.
abstract: Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Nickolas H
authors.initials: NH
authors.lastname: Anderson
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Centre, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Samuel O
authors.initials: SO
authors.lastname: Odoh
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Centre, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Yiyi
authors.initials: Y
authors.lastname: Yao
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Ursula J
authors.initials: UJ
authors.lastname: Williams
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Brian A
authors.initials: BA
authors.lastname: Schaefer
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: John J
authors.initials: JJ
authors.lastname: Kiernicki
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Lewis
authors.affiliation: Department of Chemistry, University of Missouri, Columbia, Missouri 65211, USA.
authors.forename: Mitchell D
authors.initials: MD
authors.lastname: Goshert
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 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, Pennsylvania 19104, USA.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter
authors.affiliation: Department of Chemistry, University of Missouri, Columbia, Missouri 65211, USA.
authors.forename: Justin R
authors.initials: JR
authors.lastname: Walensky
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Centre, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Suzanne C
authors.initials: SC
authors.lastname: Bart