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La Pierre Group

@f-orbitals.bsky.social

Student Run Bluesky of the La Pierre Group at the Georgia Institute of Technology https://www.lapierregroup.com/ https://www.trucorechemistry.com/

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Andrew Boggiano@acboggiano.bsky.social · 2y ago

My new study featuring a series of uranium in the +4/+5/+6 oxidation states. I've been very intrigued by the prospect of isolating this unusual tetrahomoleptic U6+ di BArF salt for some time, and am happy to share it in IC! s/o to my co authors! chemsky⚗️ pubs.acs.org/doi/10.1021/...

U4+/5+/6+ in a Conserved Pseudotetrahedral Imidophosphorane Coordination Sphere

While several ligand systems support uranium across a range of oxidation states, spanning more than two oxidation states in a conserved coordination geometry is uncommon among structurally authenticated complexes. Imidophosphorane ligands significantly stabilize high-valent lanthanide and actinide complexes. Here, we report a series of homoleptic uranium imidophosphorane complexes, spanning the +4, +5 and +6 oxidation states in a four-coordinate pseudotetrahedral ligand field. The +6 oxidation state is accessible using a mild ferrocenium oxidant, yielding a rare example of U6+ in a pseudotetrahedral coordination environment. As the formal oxidation state increases, the U–N distances gradually contract, consistent with the Shannon ionic radii of U4+/5+/6+. Compared to reported complexes, the short U–N distances observed in the U6+ complex are more comparable to dianionic imido ligands than monoanionic amido ligands.

pubs.acs.org