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Dau PD, Carretas JM, Marçalo J, et al. Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite. Inorg Chem. 2015;54(17):8755-60doi: 10.1021/acs.inorgchem.5b01385.
Dau, P. D., Carretas, J. M., Marçalo, J., Lukens, W. W., & Gibson, J. K. (2015). Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite. Inorganic chemistry, 54(17), 8755-60. https://doi.org/10.1021/acs.inorgchem.5b01385
Dau, Phuong D, et al. "Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite." Inorganic chemistry vol. 54,17 (2015): 8755-60. doi: https://doi.org/10.1021/acs.inorgchem.5b01385
Dau PD, Carretas JM, Marçalo J, Lukens WW, Gibson JK. Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite. Inorg Chem. 2015 Sep 08;54(17):8755-60. doi: 10.1021/acs.inorgchem.5b01385. Epub 2015 Aug 14. PMID: 26273901.
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Inorg Chem. 2015 Sep 08;54(17):8755-60. doi: 10.1021/acs.inorgchem.5b01385. Epub 2015 Aug 14.

Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite.

Inorganic chemistry

Phuong D Dau, José M Carretas, Joaquim Marçalo, Wayne W Lukens, John K Gibson

Affiliations

  1. Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
  2. Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa , 2695-066 Bobadela LRS, Portugal.

PMID: 26273901 DOI: 10.1021/acs.inorgchem.5b01385

Abstract

The gas-phase complexes AnO2(CH3CO2)2(-) are actinyl(V) cores, An(V)O2(+) (An = U, Np, Pu), coordinated by two acetate anion ligands. Whereas the addition of O2 to U(V)O2(CH3CO2)2(-) exothermically produces the superoxide complex U(VI)O2(O2)(CH3CO2)2(-), this oxidation does not occur for Np(V)O2(CH3CO2)2(-) or Pu(V)O2(CH3CO2)2(-) because of the higher reduction potentials for Np(V) and Pu(V). It is demonstrated that NO2 is a more effective electron-withdrawing oxidant than O2, with the result that all three An(V)O2(CH3CO2)2(-) exothermically react with NO2 to form nitrite complexes, An(VI)O2(CH3CO2)2(NO2)(-). The assignment of the NO2(-) anion ligand in these complexes, resulting in oxidation from An(V) to An(VI), is substantiated by the replacement of the acetate ligands in AnO2(CH3CO2)2(NO2)(-) and AnO2(CH3CO2)3(-) by nitrites, to produce the tris(nitrite) complexes AnO2(NO2)3(-). The key chemistry of oxidation of An(V) to An(VI) by the addition of neutral NO2 is established by the substitution of acetate by nitrite. The replacement of acetate ligands by NO2(-) is attributed to a metathesis reaction with nitrous acid to produce acetic acid and nitrite.

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