Journal article
Photochemical Synthesis and Characterization of a Uranyl Peroxide Triethylamine N‐OxideDimer
European journal of inorganic chemistry, Vol.27(28), e202400300
10/01/2024
DOI: 10.1002/ejic.202400300
Appears in UI Libraries Support Open Access
Abstract
A µ‐peroxido‐bis[di‐triethylamine N‐oxide‐dichloro‐dioxouranium] complex with the formula [(UO2)2O2(ON(CH2CH3)3)4Cl2] (complex 1) was synthesized photochemically from a reaction containing uranyl chloride, triethylamine, and H2O2. The photochemical breakdown of H2O2 yielded •OH radicals that reacted with triethylamine to form triethylamine N‐oxide (TEAO) in situ, which subsequently coordinated to UO22+ cations in a monodentate fashion via the N‐oxide functional groups. Structure determination using single crystal X‐ray diffraction revealed that TEAO ligands also formed intermolecular and intramolecular hydrogen bonds with UO22+ and peroxide moieties, and the intermolecular H‐bonding interactions displayed a temperature dependence with Oyl ‐ ‐ H – C and Oper ‐ ‐ H – C distances shortening at 100(2) K by ca. 0.1 Å. Raman spectroscopy data were collected on single crystals of 1 and peak fitting of these results allowed for assignments of peaks including C‐N stretches for TEAO ligands bound to UO22+ cations at 696.8 cm‐1, 717.8 cm‐1, and 776.5 cm‐1, which are redshifted by approximately 30 cm‐1 when compared to free triethylamine. UO22+ν1 and O22‐ν1 stretches, U‐Oper stretches, and notably, U‐Cl stretches were all identified as well, with U‐Cl modes at 198.9 cm‐1 and 212.1 cm‐1 substantially redshifted compared to the uranyl chloride starting material.
Details
- Title: Subtitle
- Photochemical Synthesis and Characterization of a Uranyl Peroxide Triethylamine N‐OxideDimer
- Creators
- Brett Lottes - University of IowaKorey P. Carter - University of Iowa
- Resource Type
- Journal article
- Publication Details
- European journal of inorganic chemistry, Vol.27(28), e202400300
- DOI
- 10.1002/ejic.202400300
- ISSN
- 1434-1948
- eISSN
- 1099-0682
- Publisher
- Wiley; WEINHEIM
- Grant note
- University of IowaCollege of Liberal Arts and SciencesDepartment of Chemistry at the University of Iowa: CHE-1828117 University of Iowa Materials, Analysis, Testing - NSF
The work was supported by start-up funding from the College of Liberal Arts and Sciences and the Department of Chemistry at the University of Iowa. We acknowledge the University of Iowa Materials, Analysis, Testing, and Fabrication Facility for use of the single crystal X-ray diffractometer and Raman microscope used in this study. Single crystal XRD data was collected on an instrument funded by NSF Award CHE-1828117.
- Language
- English
- Electronic publication date
- 07/15/2024
- Date published
- 10/01/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984658348702771
Metrics
4 Record Views