[Tetraamminecadmium(II)] bis(permanganate) (1) was prepared and its crystal structure was elucidated with XRD-Rietveld refinement and vibrational spectroscopic methods. Compound 1 has a cubic lattice consisting of a 3D hydrogen-bonded network built as four by four distorted tetrahedral blocks of [Cd(NH 3) 4] 2+ cations and MnO 4 - anions, respectively. The other four permanganate ions are located in a crystallographically different environment, placed in the cavities formed by the attachment of the building blocks. A low-temperature (≈100 °C) solid phase quasi-intramolecular redox reaction producing ammonium nitrate and amorphous CdMn 2O 4 could be established. Neither solid phase nor aqueous solution phase thermal deammoniation of compound 1 can be used to prepare Cd(MnO 4) 2 and [Cd(NH 3) 2(MnO 4) 2]. During deammoniation of compound 1 in aqueous solution a precipitate consisting of Cd(OH) 2 forms. Additionally, solid MnO 2 and ammonium permanganate (NH 4MnO 4) forms. The solid phase deammoniation reaction (toluene used as heat convecting medium) with subsequent aqueous leaching of the ammonium nitrate formed has proved to be an easy and convenient technique for the synthesis of amorphous CdMn 2O 4+x type NO x and MeSH sensor precursors. The 1-D perdeuterated complex was also synthesized to distinguish the N-H(D) and O-H(D) fragment signals in the TG-MS spectra and to elucidate the vibrational characteristics of the overlapping Mn-O and Cd-N frequencies.
|Number of pages||10|
|Journal||Zeitschrift fur Anorganische und Allgemeine Chemie|
|Publication status||Published - jan. 1 2012|
ASJC Scopus subject areas
- Inorganic Chemistry