Synthesis, structure, and Mössbauer spectroscopic studies on the heat-induced solid-phase redox reactions of hexakis(urea-O)iron(III) peroxodisulfate

Abstract

Anhydrous hexakis(urea-O)iron(III)]peroxydisulfate ([Fe(urea-O)6]2(S2O8)3 (compound 1), and its deuterated form were prepared and characterized with single-crystal X-ray diffraction and spectroscopic (IR, Raman, UV, and Mössbauer) methods. Six crystallographically different urea ligands coordinate via their oxygen in a propeller-like arrangement to iron(III) forming a distorted octahedral complex cation. The octahedral arrangement of the complex cation and its packing with two crystallographically different persulfate anions is stabilized by extended intramolecular (N–H⋯O = C) and intermolecular (N–H⋯O–S) hydrogen bonds. The two types of peroxydisulfate anions form different kinds and numbers of hydrogen bonds with the neighboring [hexakis(urea-O)6iron(III)]3+ cations. There are spectroscopically six kinds of urea and three kinds (2 + 1) of persulfate ions in compound 1, thus to distinguish the overlapping bands belonging to internal and external vibrational modes, deuteration of compound 1 and low-temperature Raman measurements were also carried out, and the bands belonging to the vibrational modes of urea and persulfate ions have been assigned. The thermal decomposition of compound 1 was followed by TG-MS and DSC methods in oxidative and inert atmospheres as well. The decomposition starts at 130 °C in inert atmosphere with oxidation of a small part of urea (~ 1 molecule), which supports the heat demand of the transformation of the remaining urea into ammonia and biuret/isocyanate. The next step of decomposition is the oxidation of ammonia into N2 along with the formation of SO2 (from sulfite). The main solid product proved to be (NH4)3Fe(SO4)3 in air. In inert atmosphere, some iron(II) compound also formed. The thermal decomposition of (NH4)3Fe(SO4)3 via NH4Fe(SO4)2 formation resulted in α-Fe2O3. The decomposition pathway of NH4Fe(SO4)2, however, depends on the experimental conditions. NH4Fe(SO4)2 transforms into Fe2(SO4)3, N2, H2O, and SO2 at 400 °C, thus the precursor of α-Fe2O3 is Fe2(SO4)3. Above 400 °C (at isotherm heating), however, the reduction of iron(III) centers was also observed. FeSO4 formed in 27 and 75% at 420 and 490 °C, respectively. FeSO4 also turns into α-Fe2O3 and SO2 on further heating. Graphical abstract: [Figure not available: see fulltext.]