Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO2(C2O4)2]3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]
Abstract
The kinetics of ligand exchange between the free oxalate ion, C2O42-, and the bis-oxalato NpV complex, [NpO2(C2O4)2]3-, in aqueous solution are reported by using 13C and 17O NMR spectroscopy methods. Rates of exchange were measured in the pH regime of 6.5–9.0, at which speciation is shown to be suitably simple. Because the neptunium(V) complex is paramagnetic, the rates of ligand exchange were estimated by following the width of the 13C and 17O signals assigned to the free oxalate ion in solution and by applying the Swift–Connick method for measuring rates of exchange. A set of experiments were conducted in which pH and total oxalate concentration were varied, and the linear dependence of the rate on these parameters was demonstrated. Variable-temperature NMR spectroscopy was also performed to measure activation parameters of complexation. Finally, at pH<8.0, ΔH≠=16.9 ±4.9 kJ mol-1 and ΔS≠=-116.3 ±17.1kJ mol-1K-1, whereas at pH>8.0 there is almost no dependence on temperature, which is interpreted to indicate that hydrolysis is coupled to ligand exchange under these conditions.
- Authors:
-
[1];
[1]
- Univ. of California, Davis, CA (United States). Dept. of Chemistry
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1466938
- Alternate Identifier(s):
- OSTI ID: 1423490
- Report Number(s):
- LLNL-JRNL-744744
Journal ID: ISSN 2192-6506; 899908
- Grant/Contract Number:
- AC52-07NA27344; SC0001089
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemPlusChem
- Additional Journal Information:
- Journal Volume: 83; Journal Issue: 7; Journal ID: ISSN 2192-6506
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; kinetics; ligand effects; neptunium; NMR spectroscopy; radiochemistry
Citation Formats
Pilgrim, Corey D., Mason, Harris E., Zavarin, Mavrik, and Casey, William H. Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO2(C2O4)2]3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]. United States: N. p., 2018.
Web. doi:10.1002/cplu.201800025.
Pilgrim, Corey D., Mason, Harris E., Zavarin, Mavrik, & Casey, William H. Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO2(C2O4)2]3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]. United States. https://doi.org/10.1002/cplu.201800025
Pilgrim, Corey D., Mason, Harris E., Zavarin, Mavrik, and Casey, William H. Fri .
"Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO2(C2O4)2]3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]". United States. https://doi.org/10.1002/cplu.201800025. https://www.osti.gov/servlets/purl/1466938.
@article{osti_1466938,
title = {Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO2(C2O4)2]3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]},
author = {Pilgrim, Corey D. and Mason, Harris E. and Zavarin, Mavrik and Casey, William H.},
abstractNote = {The kinetics of ligand exchange between the free oxalate ion, C2O42-, and the bis-oxalato NpV complex, [NpO2(C2O4)2]3-, in aqueous solution are reported by using 13C and 17O NMR spectroscopy methods. Rates of exchange were measured in the pH regime of 6.5–9.0, at which speciation is shown to be suitably simple. Because the neptunium(V) complex is paramagnetic, the rates of ligand exchange were estimated by following the width of the 13C and 17O signals assigned to the free oxalate ion in solution and by applying the Swift–Connick method for measuring rates of exchange. A set of experiments were conducted in which pH and total oxalate concentration were varied, and the linear dependence of the rate on these parameters was demonstrated. Variable-temperature NMR spectroscopy was also performed to measure activation parameters of complexation. Finally, at pH<8.0, ΔH≠=16.9 ±4.9 kJ mol-1 and ΔS≠=-116.3 ±17.1kJ mol-1K-1, whereas at pH>8.0 there is almost no dependence on temperature, which is interpreted to indicate that hydrolysis is coupled to ligand exchange under these conditions.},
doi = {10.1002/cplu.201800025},
journal = {ChemPlusChem},
number = 7,
volume = 83,
place = {United States},
year = {2018},
month = {3}
}
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Figure 1: A representative absorbance spectrum of the mixture of NpO2(C2O4)- and NpO2(C2O4)3- in aqueous solution, with no free NpO2+ seen.
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