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)

Journal Article · Wed May 15 00:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00010a018· OSTI ID:5942467

Yunlu, Kenan; Gradeff, P S; Edelstein, N; Kot, W; Shalimoff, G; Streib, W E; Vaartstra, B A; Caulton, K G ^[1]

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1. 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), Vol. 30:10; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKOXIDES
CRYSTAL STRUCTURE
CERIUM COMPLEXES
REDUCTION
OXYGEN COMPOUNDS
PRASEODYMIUM COMPLEXES
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
MAGNETIC SUSCEPTIBILITY
PHOTOCHEMISTRY
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
INFORMATION
MAGNETIC PROPERTIES
MAGNETIC RESONANCE
NUMERICAL DATA
PHYSICAL PROPERTIES
RARE EARTH COMPLEXES
RESONANCE
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry