Transuranic organometallics: The next generation
Neptunium and plutonium metal react cleanly with 3/2 equiv. I{sub 2} in aprotic ligating solvents, L, such as tetrahydrofuran (THF), pyridine (Py), and dimethylsulfoxide (DMSO) to give the triiodide complexes as tetrasolvates, AnI{sub 3}(L){sub 4} (An = Np, L = THF (1)); An = Pu, L = THF (2a), Py (2b), and DMSO (2c). These triiodide complexes are convenient precursors to new transuranic compounds. Reaction of the triiodide complexes 1 and 2a hexane with 3 equiv. of sodium bis(trimethylsilyl)amide give the volatile, solvate-free tris(silylamide) complexes, An(N(SiMe{sub 3}){sub 2}){sub 3} (An = Np, 3; An = Pu, 4). The silylamide complexes 3 and 4 undergo rapid reaction in hexane upon stoichiometric addition of HO-2,6-(t-C{sub 4}H{sub 9}){sub 2}C{sub 6}H{sub 3} to give the aryl oxide complexes An(O-2,6-(t-C{sub 4}H{sub 9}){sub 2}C{sub 6}H{sub 3}){sub 3} (An = Np, 5; An = Pu, 6). Preliminary investigations suggest that the aryl oxide complexes 5 and 6 react with lithium bis(trimethylsilyl)methanide, Li{sup +} CH(SiMe{sub 3}){sub 2}, in hexane to give the homoleptic alkyl complexes An(CH(SiMe{sub 3}){sub 2}){sub 3} (An = Np, 7; An = Pu, 8). The homoleptic silylamide, aryl oxide, and alkyl complexes are the first to be reported for transuranic elements. 17 refs.
- Research Organization:
- Los Alamos National Lab., NM (USA)
- Sponsoring Organization:
- DOE/DP
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 6807288
- Report Number(s):
- LA-UR-90-3264; CONF-900846-4; ON: DE91000212
- Resource Relation:
- Conference: International symposium to commemorate the 50th anniversary of discovery of transuranium elements, Washington, DC (USA), 26-31 Aug 1990
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
IODIDES
CHEMICAL PREPARATION
NEPTUNIUM COMPLEXES
PLUTONIUM COMPLEXES
DMSO
HEXANE
ORGANOMETALLIC COMPOUNDS
OXIDES
PYRIDINE
TETRAHYDROFURAN
ACTINIDE COMPLEXES
ALKANES
AZINES
CHALCOGENIDES
COMPLEXES
FURANS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
IODINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PYRIDINES
SULFOXIDES
SYNTHESIS
TRANSURANIUM COMPLEXES
400201* - Chemical & Physicochemical Properties
400700 - Radiochemistry & Nuclear Chemistry