Journal article
Quantifying the Influence of Covalent Metal-Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes
Angewandte Chemie (International ed.), Vol.61(45), e202211145
09/12/2022
DOI: 10.1002/anie.202211145
Appears in UI Libraries Support Open Access
Abstract
Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal-ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U3+ and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalent f-metals that show how shorter-than-expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal-ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.
Details
- Title: Subtitle
- Quantifying the Influence of Covalent Metal-Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes
- Creators
- Taylor V Fetrow - University of IowaJoshua Zgrabik - University of IowaRina Bhowmick - University of South DakotaFrancesca D Eckstrom - University of IowaGeorge Crull - University of IowaBess Vlaisavljevich - University of South DakotaScott R Daly - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Angewandte Chemie (International ed.), Vol.61(45), e202211145
- DOI
- 10.1002/anie.202211145
- eISSN
- 1521-3773
- Publisher
- Wiley
- Grant note
- DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DESC0019426; DOI: 10.13039/100000165, name: Division of Chemistry, award: CHE-1828117, CHE-2017828; DOI: 10.13039/100000001, name: National Science Foundation, award: OAC-1626516
- Language
- English
- Date published
- 09/12/2022
- Academic Unit
- Chemistry
- Record Identifier
- 9984297352702771
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