Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)

Ogden, Mark; Hoch, Courtney L; Sinkov, Sergey I; Meier, Patrick; Lumetta, Gregg J; Nash, Kenneth L

doi:10.1007/s10953-011-9762-7

Title: Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)

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Abstract

A new bidentate nitrogen donor complexing agent that combines pyridine and triazole functional groups, 2-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)pyridine (PTMP), has been synthesized. The strength of its complexes with trivalent americium (Am3+) and neodymium (Nd3+) in anhydrous methanol has been evaluated using spectrophotometric techniques. The purpose of this investigation is to assess this ligand (as representative of a class of similarly structured species) as a possible model compound for the challenging separation of trivalent actinides from lanthanides. This separation, important in the development of advanced nuclear fuel cycles, is best achieved through the agency of multidentate chelating agents containing some number of nitrogen or sulfur donor groups. To evaluate the relative strength of the bidentate complexes, the derived constants are compared to those of the same metal ions with 2,2*-bipyridyl (bipy), 1,10-phenanthroline (phen), and 2-pyridin-2-yl-1H-benzimidazole (PBIm). At issue is the relative affinity of the triazole moiety for trivalent f element ions. For all ligands, the derived stability constants are higher for Am3+ than Nd3+. In the case of Am3+ complexes with phen and PBIm, the presence of 1:2 (AmL2) species is indicated. Possible separations are suggested based on the relative stability and stoichiometry of the Am3+ and Nd3+ complexes. It can be noted thatmore »« less

Authors:: Ogden, Mark; Hoch, Courtney L; Sinkov, Sergey I; Meier, Patrick; Lumetta, Gregg J; Nash, Kenneth L

Publication Date:: Mon Nov 28 00:00:00 EST 2011

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1038648

Report Number(s):: PNNL-SA-85240
Journal ID: ISSN 0095-9782; JSLCAG; 830403000; TRN: US1201935

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Journal of Solution Chemistry

Additional Journal Information:: Journal Volume: 40; Journal Issue: 11; Journal ID: ISSN 0095-9782

Country of Publication:: United States

Language:: English

Subject:: 10 SYNTHETIC FUELS; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; ACTINIDES; AFFINITY; AMERICIUM; CHELATING AGENTS; FUNCTIONALS; METHANOL; NEODYMIUM; NITROGEN; NUCLEAR FUELS; PYRIDINE; RARE EARTHS; STABILITY; STOICHIOMETRY; SULFUR; TRIAZOLES; Complexation; Am(III); Nd(III); Bidentate heterocyclic N-donor ligands; Anhydrous methanol media; Spectrophotometry; LANTHANIDE(III) COMPLEXES; TRIVALENT ACTINIDES; SOLUTION CHEMISTRY; NITROGEN LIGANDS; SEPARATION; EXTRACTION; LANTHANIDES(III); AMERICIUM(III); TPEN

Citation Formats


                    Ogden, Mark, Hoch, Courtney L, Sinkov, Sergey I, Meier, Patrick, Lumetta, Gregg J, and Nash, Kenneth L. Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III).  United States: N. p., 2011. 
        Web.  doi:10.1007/s10953-011-9762-7.

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                    Ogden, Mark, Hoch, Courtney L, Sinkov, Sergey I, Meier, Patrick, Lumetta, Gregg J, & Nash, Kenneth L. Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III).  United States.  https://doi.org/10.1007/s10953-011-9762-7

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                    Ogden, Mark, Hoch, Courtney L, Sinkov, Sergey I, Meier, Patrick, Lumetta, Gregg J, and Nash, Kenneth L. 2011.  
        "Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)".  United States.  https://doi.org/10.1007/s10953-011-9762-7.

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@article{osti_1038648,

  title        = {Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)},

  author       = {Ogden, Mark and Hoch, Courtney L and Sinkov, Sergey I and Meier, Patrick and Lumetta, Gregg J and Nash, Kenneth L},

  abstractNote = {A new bidentate nitrogen donor complexing agent that combines pyridine and triazole functional groups, 2-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)pyridine (PTMP), has been synthesized. The strength of its complexes with trivalent americium (Am3+) and neodymium (Nd3+) in anhydrous methanol has been evaluated using spectrophotometric techniques. The purpose of this investigation is to assess this ligand (as representative of a class of similarly structured species) as a possible model compound for the challenging separation of trivalent actinides from lanthanides. This separation, important in the development of advanced nuclear fuel cycles, is best achieved through the agency of multidentate chelating agents containing some number of nitrogen or sulfur donor groups. To evaluate the relative strength of the bidentate complexes, the derived constants are compared to those of the same metal ions with 2,2*-bipyridyl (bipy), 1,10-phenanthroline (phen), and 2-pyridin-2-yl-1H-benzimidazole (PBIm). At issue is the relative affinity of the triazole moiety for trivalent f element ions. For all ligands, the derived stability constants are higher for Am3+ than Nd3+. In the case of Am3+ complexes with phen and PBIm, the presence of 1:2 (AmL2) species is indicated. Possible separations are suggested based on the relative stability and stoichiometry of the Am3+ and Nd3+ complexes. It can be noted that the 1,2,3-triazolyl group imparts a potentially useful selectivity for trivalent actinides (An(III)) over trivalent lanthanides (Ln(III)), though the attainment of higher complex stoichiometries in actinide compared with lanthanide complexes may be an important driver for developing successful separations.},

  doi          = {10.1007/s10953-011-9762-7},

  url          = {https://www.osti.gov/biblio/1038648},
  journal      = {Journal of Solution Chemistry},

  issn         = {0095-9782},

  number       = 11,

  volume       = 40,

  place        = {United States},

  year         = {Mon Nov 28 00:00:00 EST 2011},

  month        = {Mon Nov 28 00:00:00 EST 2011}

}

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