Journal article
Solution Spectroscopic Analysis of Ligand Exchange in Uranium Mono-Oxo Complexes
Inorganic chemistry
10/06/2026
DOI: 10.1021/acs.inorgchem.6c03607
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.
Details
- Title: Subtitle
- Solution Spectroscopic Analysis of Ligand Exchange in Uranium Mono-Oxo Complexes
- Creators
- Florian Ressnik - Georgia Institute of TechnologyTyler-Rayne Nero - Georgia Institute of TechnologyMaximilian G. Bernbeck - Georgia Institute of TechnologyJohannes Leisen - Georgia Institute of TechnologyBess Vlaisavljevich - University of IowaJulie E. Niklas - Georgia Institute of TechnologyHenry S. La Pierre - Georgia Institute of Technology
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry
- DOI
- 10.1021/acs.inorgchem.6c03607
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Publisher
- American Chemical Society
- Grant note
- U.S. Department of Energy: DE-SC0019385
Experimental and spectroscopic studies at GT were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program under Award Number DE-SC0019385 (F.R., T.-R.N., J.E.N., H.S.L.P.). Computational studies were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, in the Heavy Element Chemistry program under Award Number DE-SC0025311 (B.V.). B.V. also thanks the University of Iowa for start-up funds supporting computational resources. The authors thank Dr. Hongwei Wu for assistance with low-temperature NMR measurements, Dr. Florian Kleemiss for advice on crystallographic refinements, and Nathan Loutsch for discussion of DFT NMR computations.
- Language
- English
- Electronic publication date
- 10/06/2026
- Academic Unit
- Chemistry
- Record Identifier
- 9985243570602771
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