Plutonium (III) and uranium (III) nitrile complexes
Conference
·
OSTI ID:976234
- Alejandro E.
- John H.
- Brian L.
- Mary P.
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.
- Research Organization:
- Los Alamos National Laboratory
- Sponsoring Organization:
- DOE
- OSTI ID:
- 976234
- Report Number(s):
- LA-UR-02-4582
- Country of Publication:
- United States
- Language:
- English
Similar Records
A convenient entry into trivalent actinide chemistry: Synthesis and characterization of AnI{sub 3}(THF){sub 4} and An[N(SiMe{sub 3}){sub 2}]{sub 3} (An = U, Np, Pu)
Synthesis, characterization, and X-ray structure of ([K(THF)[sub 2]][sub 2][U(NH-2,6-i-Pr[sub 2]C[sub 6]H[sub 3])[sub 5]]) [center dot] THF
New dicarbollide complexes of uranium
Journal Article
·
Wed May 11 00:00:00 EDT 1994
· Inorganic Chemistry
·
OSTI ID:450857
Synthesis, characterization, and X-ray structure of ([K(THF)[sub 2]][sub 2][U(NH-2,6-i-Pr[sub 2]C[sub 6]H[sub 3])[sub 5]]) [center dot] THF
Journal Article
·
Wed May 13 00:00:00 EDT 1992
· Inorganic Chemistry; (United States)
·
OSTI ID:6975311
New dicarbollide complexes of uranium
Journal Article
·
Tue Mar 12 23:00:00 EST 1996
· Inorganic Chemistry
·
OSTI ID:263757