Harnessing redox activity for the formation of uranium tris(imido) compounds

Nat Chem. 2014 Oct;6(10):919-26. doi: 10.1038/nchem.2009. Epub 2014 Jul 27.

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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

Associated data

  • PubChem-Substance/187874776
  • PubChem-Substance/187874777
  • PubChem-Substance/187874778
  • PubChem-Substance/187874779
  • PubChem-Substance/187874780
  • PubChem-Substance/187874781
  • PubChem-Substance/187874782
  • PubChem-Substance/187874783