f-Element/crown ether complexes. 10. Oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus// in the presence of crown ethers: Structural characterization of crown ether complexed ammonium ions ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN and synthesis of (Na(12-crown-4)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe
Trace amounts of H/sub 2/O and limited exposure to air of reaction mixtures of UCl/sub 4/ and 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, or dibenzo-18-crown-6 in 1:3 mixtures of CH/sub 3/OH and CH/sub 3/CN resulted in the hydrolysis and oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus//. In the presence of these crown ethers, it has been possible to isolate intermediate products via crystallization of crown complexes of the (UO/sub 2/Cl/sub 4/)/sup 2/minus// ion, the (UCl/sub 6/)/sup 2/minus// ion, and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/). The neutral moiety crystallizes as a hydrogen-bonded crown ether complex; however, crown ether complexation of a counterion, either an ammonium ion formed during the oxidation of U(IV) or a Na/sup +/ ion leached from glass reaction vessels, resulted in novel crystalline complexes of the ionic species. ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN have been structurally characterized by single-crystal X-ray diffraction techniques. The results of all the crystal studies are presented in detail. The ammonium ions interact with the crown ethers via hydrogen-bonding and electrostatic interactions. 15-Crown-5 and benzo-15-crown-5 form 2:1 sandwich cations, allowing no H/sub 4/N/sup +//hor ellipsis/(UO/sub 2/Cl/sub 4/)/sup 2/minus// interaction. The dibenzo-18-crown-6 complexed ammonium ions are 1:1 and form bifurcated hydrogen bonds with the chlorine atoms in the (UO/sub 2/Cl/sub 4/)/sup /minus// anion. The formation of (Na(12-crown-4)/sub 2//sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH)/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe has been confirmed by preliminary single-crystal X-ray diffraction studies.
- Research Organization:
- Northern Illinois Univ., DeKalb (USA)
- OSTI ID:
- 5844759
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:26; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis and structural characterization of the monodentate 12-crown-4 and hexaethylene glycol complexes of uranium(VI): [UO[sub 2]Cl[sub 2](OH[sub 2])[sub 2](12-crown-4)][center dot]12-crown-4 and UO[sub 2]Cl[sub 2](OH[sub 2])[sub 2](hexaethylene glycol)
Controlling the primary coordination sphere: Complexation of the 4f-elements by crown ethers as models for potential extraction systems
Related Subjects
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
ALCOHOLS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
CRYSTAL STRUCTURE
CYANIDES
DATA
DECOMPOSITION
EXPERIMENTAL DATA
GLYCOLS
HALIDES
HALOGEN COMPOUNDS
HYDROLYSIS
HYDROXY COMPOUNDS
INFORMATION
LYSIS
METHANOL
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC POLYMERS
ORGANOMETALLIC COMPOUNDS
OXIDATION
POLYETHYLENE GLYCOLS
POLYMERS
SOLVOLYSIS
URANIUM CHLORIDES
URANIUM COMPOUNDS
URANYL COMPOUNDS