Solution Spectroscopic Analysis of Ligand Exchange in Uranium Mono-Oxo Complexes
Abstract Four uranium mono-oxo imidophosphorane complexes with a closed set of systematically changed substituents (pyrrolidine vs piperidine and introduction of one tert-butyl group) are presented. All complexes exhibit an inverse trans-influence (ITI). The rapid exchange of axial and equatorial ligands at room temperature, the unique 31P nuclear magnetic resonance (NMR) handle of the ligands, and the complexes’ overall closed-shell singlet ground state facilitate the determination of ligand-exchange barriers via variable-temperature (VT) and exchange spectroscopy (EXSY) NMR. Computational analysis delineates electronic and steric contributions to the experimentally determined exchange barriers.
Authors
- Bess Vlaisavljevich (ORCID: https://orcid.org/0000-0001-6065-0732)
- Henry S. La Pierre (ORCID: https://orcid.org/0000-0002-0895-0655)
- Julie E. Niklas (ORCID: https://orcid.org/0000-0002-4132-3733)
- Maximilian G. Bernbeck (ORCID: https://orcid.org/0000-0001-6329-5860)
- Johannes Leisen (ORCID: https://orcid.org/0000-0003-0474-670X)
- Florian Ressnik (ORCID: https://orcid.org/0009-0003-9720-8421)
- Tyler-Rayne Nero (ORCID: https://orcid.org/0009-0000-2951-6615)
Institutions
- University of Iowa (US)
- Georgia Institute of Technology (US)
- Pacific Northwest National Laboratory (US)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2026-10-06
- DOI
- https://doi.org/10.1021/acs.inorgchem.6c03607
- Primary Topic
- Radioactive element chemistry and processing
- Type
- article
- Field-Weighted Citation Impact
- 0.00