Complex peroxyuranates. Synthesis and structural assessment of alkali dioxoxperoxy(sulfato)aquouranates(VI), A2[UO2(O2)SO4(H2O)] (A = NH4, Na), and alkali dioxoperoxy(oxalato)uranate(VI) hydrates, A2[UO2(O2)C2O4].H2O

Bhattacharjee, Manish ; Chaudhuri, Mihir K. ; Purkayastha, Ranendra N. Dutta (1986) Complex peroxyuranates. Synthesis and structural assessment of alkali dioxoxperoxy(sulfato)aquouranates(VI), A2[UO2(O2)SO4(H2O)] (A = NH4, Na), and alkali dioxoperoxy(oxalato)uranate(VI) hydrates, A2[UO2(O2)C2O4].H2O Inorganic Chemistry, 25 (14). pp. 2354-2357. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic00234a016

Related URL: http://dx.doi.org/10.1021/ic00234a016

Abstract

Yellow microcrystalline alkali-metal and ammonium dioxoperoxy(sulfato)aquouranates(VI), A2(UO2(O2)SO 4(H2O)) (A = NH4, Na), and alkali-metal and ammonium dioxoperoxy(oxalato)uranate(VI) hydrates, A2UO 2(O2)C2O).H2O (A = NH4, Na, K), have been synthesized from the reaction of the product obtained by treating an aqueous solution of UO2(NO3)2.6H2O with alkali-metal or ammonium hydroxide, AOH, with 30% H2O2 and aqueous sulfuric acid and oxalic acid solution, respectively, in the mole ratio UO2(NO3)2.6H2O:H2O2:SO42 - or C2O42- of 1:111:5 or 1, at pH 6 maintained by the addition of the corresponding alkali-metal or ammonium hydroxide. Precipitation was completed by the addition of ethanol. IR and laser Raman spectra suggest that the O22 - and SO42 - ions in (UO2(O2)SO4(H2O))2- are bonded to the UO22 + center in a bridging and in a monodentate manner, respectively, while both the O22 - and C2O42 - ions in (UO2(O2)C2O) 2 - bind the uranyl center in bidentate chelated fashion. The complex peroxyuranates are diamagnetic and insoluble. The A2(UO2(O2)SO4(H2O)) compounds, unlike A2(UO2(O2)C2O4).H2O, are stable up to 110°C. Whereas H2O in A2(UO(O2SO4(H2O)) is coordinated to the UO22+ center, it occurs as a water of crystallization in the corresponding peroxy oxalato compounds.

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