University of Minnesota
University of Minnesota

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Harnessing redox activity for the formation of uranium compounds

Classically, 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.

A collaborative effort between the experimental research group of Suzanne Bart at Purdue University, and the computational group of Laura Gagliardi at the University of Minnesota has shown significant progress in this direction. Participating in the study were post-doctoral associate Samuel Odoh, Ph.D., and Yiyi Yao, a graduate student from the University of Minnesota, and several students from Purdue University.

A paper by these groups that appeared, July 27, 2014, in Nature Chemistry shows 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. 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) and its tris(oxo) analogue.