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Complex peroxyuranates. Synthesis and structural assessment of alkali-metal and ammonium dioxoperoxy(sulfato)aquouranates(VI), A/sub 2/(UO/sub 2/(O/sub 2/)SO/sub 4/(H/sub 2/O)) (A = NH/sub 4/, Na), and alkali-metal and ammonium dioxoperoxy(oxalato)uranate(VI) hydrates, A/sub 2/(UO/sub 2/(O/sub 2/)C/sub 2/O/sub 4/). H/sub 2/O

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00234a016· OSTI ID:5469226
Yellow microcrystalline alkali-metal and ammonium dioxoperoxy(sulfato)aquouranates(VI), A/sub 2/(UO/sub 2/(O/sub 2/)SO/sub 4/(H/sub 2/O)) (A = NH/sub 4/, Na), and alkali-metal and ammonium dioxoperoxy(oxalato)uranate(VI) hydrates, A/sub 2/(UO/sub 2/(O/sub 2/)C/sub 2/O/sub 4/).H/sub 2/O (A = NH/sub 4/, Na, K), have been synthesized from the reaction of the product obtained by treating an aqueous solution of UO/sub 2/(NO/sub 3/)/sub 2/.6H/sub 2/O with alkali-metal or ammonium hydroxide, AOH, with 30% H/sub 2/O/sub 2/ and aqueous sulfuric acid and oxalic acid solution, respectively, in the mole ratio UO/sub 2/(NO/sub 3/)/sub 2/.6H/sub 2/O:H/sub 2/O/sub 2/:SO/sub 4//sup 2 -/ or C/sub 2/O/sub 4//sup 2 -/ 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 O/sub 2//sup 2 -/ and SO/sub 4//sup 2 -/ ions in (UO/sub 2/(O/sub 2/)SO/sub 4/(H/sub 2/O))/sup 2 -/ are bonded to the UO/sub 2//sup 2 +/ center in a bridging and in a monodentate manner, respectively, while both the O/sub 2//sup 2 -/ and C/sub 2/O/sub 4//sup 2 -/ ions in (UO/sub 2/(O/sub 2/)C/sub 2/O/sub 4/)/sup 2 -/ bind the uranyl center in bidentate chelated fashion. The complex peroxyuranates are diamagnetic and insoluble. The A/sub 2/(UO/sub 2/(O/sub 2/)SO/sub 4/(H/sub 2/O)) compounds, unlike A/sub 2/(UO/sub 2/(O/sub 2/)C/sub 2/O/sub 4/).H/sub 2/O, are stable up to 110 /sup 0/C. Whereas H/sub 2/O in A/sub 2/(UO/sub 2/(O/sub 2/SO/sub 4/(H/sub 2/O)) is coordinated to the UO/sub 2//sup 2 +/ center, it occurs as a water of crystallization in the corresponding peroxy oxalato compounds. 20 references, 3 tables.
Research Organization:
North-Eastern Hill Univ., Shillong, India
OSTI ID:
5469226
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:14; ISSN INOCA
Country of Publication:
United States
Language:
English