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Title: Plutonium (III) and uranium (III) nitrile complexes

Abstract

Iodine oxidation of uranium and plutonium metals in tetrahydrofuran and pyridine form AnI{sub 3}(THF){sub 4} and AnI{sub 3}(py){sub 4} (An = Pu, U). These compounds represent convenient entries Into solution An(III) chemistry in organic solvents. Extensions of the actinide metal oxidation methodology in nitrile solvents by I{sub 2}, AgPF{sub 6}, and TIPF{sub 6} are presented here. Treatment of Pu{sup 0} in acetonitrile with iodine yields a putative PuI{sub 3}(NCMe){sub x} intermediate which can be trapped with the tripodal nitrogen donor ligand tpza (tpza = (tris[(2-pyrazinyl)methyl]amine)) and forms the eight-coordinate complex (tpza)PuI{sub 3}(NCMe). Treatment of excess U{sup 0} metal by iodine in acetonitrile afforded a brown crystalline mixed valence complex, [U(NCMe){sub 9}][UI{sub 6}][I], instead of UI{sub 3}(NCMe){sub 4}. The analogous reaction in bezonitrile forms red crystalline UI{sub 4}(NCPh){sub 4}. In contrast, treatment of UI{sub 3}(THF){sub 4} with excess acetonitrile cleanly generates [U(NCMe){sub 9}][I]{sub 3}. Oxidation of Pu{sup 0} by either TI(I) or Ag(I) hexafluorophosphate salts generates a nine-coordinate homoleptic acetonitrile adduct [Pu(NCMe){sub 9}][PF{sub 6}]{sub 3}. Attempts to oxidize U{sub 0} with these salts were unsuccessful.

Authors:
 [1];  [2];  [3];  [4]
  1. Alejandro E.
  2. John H.
  3. Brian L.
  4. Mary P.
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
976234
Report Number(s):
LA-UR-02-4582
TRN: US201009%%618
Resource Type:
Conference
Resource Relation:
Conference: Submitted to: Rare Earth Conference University of California, Davis, July 13-18, 2002
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; ACTINIDES; ADDUCTS; CHEMISTRY; IODINE; NITRILES; NITROGEN; ORGANIC SOLVENTS; OXIDATION; PLUTONIUM; PYRIDINE; RARE EARTHS; SOLVENTS; TETRAHYDROFURAN; URANIUM; VALENCE

Citation Formats

Enriquez, A E, Matonic, J H, Scott, B L, and Neu, M P. Plutonium (III) and uranium (III) nitrile complexes. United States: N. p., 2002. Web.
Enriquez, A E, Matonic, J H, Scott, B L, & Neu, M P. Plutonium (III) and uranium (III) nitrile complexes. United States.
Enriquez, A E, Matonic, J H, Scott, B L, and Neu, M P. 2002. "Plutonium (III) and uranium (III) nitrile complexes". United States. https://www.osti.gov/servlets/purl/976234.
@article{osti_976234,
title = {Plutonium (III) and uranium (III) nitrile complexes},
author = {Enriquez, A E and Matonic, J H and Scott, B L and Neu, M P},
abstractNote = {Iodine oxidation of uranium and plutonium metals in tetrahydrofuran and pyridine form AnI{sub 3}(THF){sub 4} and AnI{sub 3}(py){sub 4} (An = Pu, U). These compounds represent convenient entries Into solution An(III) chemistry in organic solvents. Extensions of the actinide metal oxidation methodology in nitrile solvents by I{sub 2}, AgPF{sub 6}, and TIPF{sub 6} are presented here. Treatment of Pu{sup 0} in acetonitrile with iodine yields a putative PuI{sub 3}(NCMe){sub x} intermediate which can be trapped with the tripodal nitrogen donor ligand tpza (tpza = (tris[(2-pyrazinyl)methyl]amine)) and forms the eight-coordinate complex (tpza)PuI{sub 3}(NCMe). Treatment of excess U{sup 0} metal by iodine in acetonitrile afforded a brown crystalline mixed valence complex, [U(NCMe){sub 9}][UI{sub 6}][I], instead of UI{sub 3}(NCMe){sub 4}. The analogous reaction in bezonitrile forms red crystalline UI{sub 4}(NCPh){sub 4}. In contrast, treatment of UI{sub 3}(THF){sub 4} with excess acetonitrile cleanly generates [U(NCMe){sub 9}][I]{sub 3}. Oxidation of Pu{sup 0} by either TI(I) or Ag(I) hexafluorophosphate salts generates a nine-coordinate homoleptic acetonitrile adduct [Pu(NCMe){sub 9}][PF{sub 6}]{sub 3}. Attempts to oxidize U{sub 0} with these salts were unsuccessful.},
doi = {},
url = {https://www.osti.gov/biblio/976234}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2002},
month = {1}
}

Conference:
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