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Article

A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate

1
Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt 2, H-1117 Budapest, Hungary
2
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Muegyetem rakpart 3, H-1111 Budapest, Hungary
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Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, 1000 Skopje, North Macedonia
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Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovi´ca 3, Novi Sad 21000, Serbia
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Szentagothai Research Centre, Environmental Analytical and Geoanalytical Research Group, University of Pécs, Ifjúság útja 20, H-7624 Pécs, Hungary
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Deuton-X Ltd., Selmeci u. 89, H-2030 Érd, Hungary
*
Author to whom correspondence should be addressed.
Academic Editor: Kazuyuki Takahashi
Inorganics 2021, 9(5), 38; https://doi.org/10.3390/inorganics9050038
Received: 3 April 2021 / Revised: 3 May 2021 / Accepted: 7 May 2021 / Published: 9 May 2021
(This article belongs to the Special Issue Redox-Active Ligand Complexes)
The reaction of ammoniacal AgNO3 solution (or aq. solution of [Ag(NH3)2]NO3) with aq. NaClO4 resulted in [Ag(NH3)2]ClO4 (compound 1). Detailed spectroscopic (correlation analysis, IR, Raman, and UV) analyses were performed on [Ag(NH3)2]ClO4. The temperature and enthalpy of phase change for compound 1 were determined to be 225.7 K and 103.04 kJ/mol, respectively. We found the thermal decomposition of [Ag(NH3)2]ClO4 involves a solid-phase quasi-intramolecular redox reaction between the perchlorate anion and ammonia ligand, resulting in lower valence chlorine oxyacid (chlorite, chlorate) components. We did not detect thermal ammonia loss during the formation of AgClO4. However, a redox reaction between the ammonia and perchlorate ion resulted in intermediates containing chlorate/chlorite, which disproportionated (either in the solid phase or in aqueous solutions after the dissolution of these decomposition intermediates in water) into AgCl and silver perchlorate. We propose that the solid phase AgCl-AgClO4 mixture eutectically melts, and the resulting AgClO4 decomposes in this melt into AgCl and O2. Thus, the final product of decomposition is AgCl, N2, and H2O. The intermediate (chlorite, chlorate) phases were identified by IR, XPS, and titrimetric methods. View Full-Text
Keywords: ammine; perchlorate; vibrational spectroscopy; redox reaction; thermal decomposition; disproportionation; chlorite; chlorate ammine; perchlorate; vibrational spectroscopy; redox reaction; thermal decomposition; disproportionation; chlorite; chlorate
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MDPI and ACS Style

Fogaça, L.A.; Bereczki, L.; Petruševski, V.M.; Barta-Holló, B.; Franguelli, F.P.; Mohai, M.; Béres, K.A.; Sajó, I.E.; Szilágyi, I.M.; Kotai, L. A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate. Inorganics 2021, 9, 38. https://doi.org/10.3390/inorganics9050038

AMA Style

Fogaça LA, Bereczki L, Petruševski VM, Barta-Holló B, Franguelli FP, Mohai M, Béres KA, Sajó IE, Szilágyi IM, Kotai L. A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate. Inorganics. 2021; 9(5):38. https://doi.org/10.3390/inorganics9050038

Chicago/Turabian Style

Fogaça, Lara A., Laura Bereczki, Vladimir M. Petruševski, Berta Barta-Holló, Fernanda P. Franguelli, Miklós Mohai, Kende A. Béres, Istvan E. Sajó, Imre M. Szilágyi, and Laszlo Kotai. 2021. "A Quasi-Intramolecular Solid-Phase Redox Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I) Perchlorate" Inorganics 9, no. 5: 38. https://doi.org/10.3390/inorganics9050038

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