Mössbauer study of the thermal decomposition of dinitrogen tetroxide solvates of iron(III) nitrate

Abstract
The thermal decomposition of the 1·5 N2O4 solvate of iron(III) nitrate, [N4O6]2+2[Fe(NO3)4], has been investigated. Four isolable intermediates, [NO]+[Fe(NO3)4], [NO2]+[Fe(NO3)4], [Fe2O(NO3)4], and [FeO(NO3)], have been characterised, the ultimate product being Fe2O3. [Fe2O(NO3)4] and [FeO(NO3)] both exhibit room temperature Mössbauer effects characteristic of polymeric lattices. The Mössbauer spectra of the complexes M+[Fe(NO3)4][M = Me4N, EtnNH4 –n(n= 1–4), N4O6 +, or NO2 +] and M+[FeCl4][M = EtnNH4 –n(n= 1–4)] all consist of a single resonance with isomeric shifts in the ranges 0·54–0·61 mm s–1 and 0·30–0·31 mm s–1, respectively. The two nitrosonium salts, [NO]+[FeX4](X = Cl, NO3), however, exhibit small quadrupole splittings (Δ= 0·36 mm s–1, X = Cl; Δ= 0·45 mm s–1, X = NO3), which are attributed to the interaction of the highly polarising nitrosonium cation with one of the ligands X.

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