Reactivity of ceric ammonium nitrate with sodium cyclopentadienide. The x-ray crystal structure of bis(dimethoxyethane)trinitratocerium

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.