Reactivity of ceric ammonium nitrate with sodium cyclopentadienide. X-ray crystal structure of Ce(NO sub 3 ) sub 3 (DME) sub 2

Journal Article · Wed Jun 28 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00312a019· OSTI ID:5093675

Gradeff, P S; Yunlu, K ^[1]; Deming, T J; Olofson, J M; Ziller, J W; Evans, W J ^[2]

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1. Rhone-Poulenc, Inc., New Brunswick, NJ (USA)
2. Univ. of California, Irvine (USA)

The reactions of ceric ammonium nitrate (CAN) with 1, 3, 5, and 6 equiv fo NaC{sub 5}H{sub 5} in THF have been examined. The 6-equiv reaction forms (C{sub 5}H{sub 5}){sub 3}Ce(THF) in > 90% yield in 30-60 min. The 5-equiv reaction forms a cyclopentadienylcerium nitrate complex, (C{sub 5}H{sub 5}){sub 2}Ce(NO{sub 3}){sub 2}Na(THF){sub 2}, which decomposes violently upon heating. The 3-equiv reaction forms a cerium(III) nitrate complex of low solubility. A dimethoxyethane (DME) derivative of the latter complex, Ce(NO{sub 3}){sub 3}(DME){sub 2}, has been characterized by x-ray crystallography. This complex crystallizes from DME at -34{degree}C in space group P2{sub 1}/n with a = 10.4404 (11) {angstrom}, b = 15.1301 (21) {angstrom}, c = 11.4023 (13) {angstrom}, {beta} = 92.431 (9){degree}, V = 1799.5 (4) {angstrom}{sup 3}, and D(calcd) = 1.87 g cm{sup {minus}3} for Z = 4. The reaction of CAN with 1 equiv of NaC{sub 5}H{sub 5} causes reduction of Ce(IV) to Ce(III). (C{sub 5}H{sub 5}){sub 3}Ce(THF) can also be made from (NH{sub 4}){sub 2}Ce(NO{sub 3}){sub 5} and 5 equiv of NaCP. A scheme describing the overall CAN/NaC{sub 5}H{sub 5} reaction system is presented. 45 refs., 1 fig., 2 tabs.

• OSTI ID: 5093675
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:13; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM NITRATES
CHEMICAL REACTIONS
CERIUM COMPOUNDS
ETHANE
ORGANIC OXYGEN COMPOUNDS
SODIUM COMPOUNDS
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
ALKALI METAL COMPOUNDS
ALKANES
AMMONIUM COMPOUNDS
DATA
HYDROCARBONS
INFORMATION
NITRATES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
RARE EARTH COMPOUNDS
400201* - Chemical & Physicochemical Properties