An Unprecedented‐Type Intramolecular Redox Reaction of Solid Tetraamminecopper(2+) Bis(permanganate) ([Cu(NH3)4](MnO4)2) – A Low‐Temperature Synthesis of Copper Dimanganese Tetraoxide‐Type (CuMn2O4) Nanocrystalline Catalyst Precursors |
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Authors: | Lá szló Kó tai,Kalyan K. Banerji,Istvá n Sajó ,Já nos Kristó f,B. Sreedhar,Sá ndor Holly,Gá bor Keresztury,Antal Rockenbauer |
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Abstract: | Tetraamminecopper(2+) bis(permanganate) ([Cu(NH3)4](MnO4)2; 1 ) was prepared, and its properties were studied in both aqueous solution and the solid phase. The presence of H‐bond interactions between the ammonia ligand of the complex cation and an O‐atom of the permanganate ion was detected by IR and Raman methods. The solid‐phase thermal deammoniation of 1 led to an unusual intramolecular redox reaction between the Mn O⋅⋅⋅H N linkage with formation of NH4NO3 and CuMn2O4‐type mixed oxides instead of stepwise deammoniation, even below 100°. The thermal deammoniation of 1 in aqueous solution led, instead of to hydrated copper(2+) bis(permanganate), to the formation of NH4MnO4 ( 2 ). Since the temperature of the thermal deammoniation of 1 is lower than the decomposition temperature of the permanganate ion, the regulated solid‐phase decomposition of 1 allowed preparation of CuMn2O4‐type oxides with mixing of copper and manganese at the atomic level. |
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