A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes
Abstract
The equilibrium constants for [NpO2M∙]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2∙Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ In3+ > Ga3+ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.
- Authors:
-
- Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Washington State Univ., Pullman, WA (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC)
- OSTI Identifier:
- 1356947
- Alternate Identifier(s):
- OSTI ID: 1596319
- Grant/Contract Number:
- AC05-00OR22725; SC0001815
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 9; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cation-cation; neptunium; high ionic strength; spectrophotometry; density functional theory
Citation Formats
Freiderich, John W., Burn, Adam G., Martin, Leigh R., Nash, Kenneth L., and Clark, Aurora E. A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.6b02369.
Freiderich, John W., Burn, Adam G., Martin, Leigh R., Nash, Kenneth L., & Clark, Aurora E. A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes. United States. https://doi.org/10.1021/acs.inorgchem.6b02369
Freiderich, John W., Burn, Adam G., Martin, Leigh R., Nash, Kenneth L., and Clark, Aurora E. Fri .
"A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes". United States. https://doi.org/10.1021/acs.inorgchem.6b02369. https://www.osti.gov/servlets/purl/1356947.
@article{osti_1356947,
title = {A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO2·M]4+ Cation–Cation Complexes},
author = {Freiderich, John W. and Burn, Adam G. and Martin, Leigh R. and Nash, Kenneth L. and Clark, Aurora E.},
abstractNote = {The equilibrium constants for [NpO2M∙]4+ (M = Al3+, In3+, Sc3+, Fe3+) in μ = 10 M nitric acid and [NpO2∙Ga]4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe3+ > Sc3+ In3+ > Ga3+ Al3+. These equilibrium constants are compared to those of previously reported values for NpO2+ complexes with Cr3+ and Rh3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicating that the NpO2+ dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.},
doi = {10.1021/acs.inorgchem.6b02369},
journal = {Inorganic Chemistry},
number = 9,
volume = 56,
place = {United States},
year = {Fri Apr 14 00:00:00 EDT 2017},
month = {Fri Apr 14 00:00:00 EDT 2017}
}
Web of Science
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Works referencing / citing this record:
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