Photoreduction of cerium (IV) in Ce sub 2 (O sup i Pr) sub 8 ( sup i PrOH) sub 2. Characterization and structure of Ce sub 4 O(O sup i Pr) sub 13 ( sup i PrOH)
- Lawrence Berkeley Lab., Berkeley, CA (United States) Indiana Univ., Bloomington (United States)
Visible irradiation of Ce{sub 2}(O{sup i}Pr){sub 8}({sup i}PrOH){sub 2} yields the mixed-valence compound Ce{sub 4}O(O{sup i}Pr){sub 13}({sup i}PrOH), characterized by {sup 1}H NMR and infrared spectra, elemental analysis, and x-ray diffraction. The structure is described as Ce{sub 4}({mu}{sub 4}{minus}O)({mu}{sub 3}{minus}O{sup i}Pr){sub 2}({mu}{sub 2}{minus}O{sup i}Pr){sub 4}-(O{sup i}Pr){sub 7}({sup i}PrOH). The Ce{sub 4}({mu}{minus}O) core has a butterfly form, with a crystallographic C{sub 2} axis that passes through the oxide ion and the center of a symmetric hydrogen bond between the coordinated alcohol and one terminal alkoxide. This photoredox reaction cannot be thermally induced and requires that hydrogen be present on the carbon {alpha} to the alkoxide oxygen. Magnetic susceptibility and EPR studies show the compound to be paramagnetic. Two temperature ranges of Curie-Weiss behavior are observed with {mu}{sub eff} = 2.7 {mu}{sub B} from 80 to 300 K. Crystal data ({minus}130C) are presented for the complex. 25 refs., 2 figs., 4 tabs.
- DOE Contract Number:
- FG02-88ER13906
- OSTI ID:
- 5942467
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:10; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKOXIDES
CERIUM COMPLEXES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
INFORMATION
MAGNETIC PROPERTIES
MAGNETIC RESONANCE
MAGNETIC SUSCEPTIBILITY
NUMERICAL DATA
OXYGEN COMPOUNDS
PHOTOCHEMISTRY
PHYSICAL PROPERTIES
PRASEODYMIUM COMPLEXES
RARE EARTH COMPLEXES
REDUCTION
RESONANCE