Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions
[κ<sup>2</sup>-O,O′-Carbonatotetraamminecobalt(III)] iodide, or [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>]I, named in this paper as compound <b>1,</b> was prepared and characterized comprehensively with spectroscopic (IR, Raman and UV)...
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MDPI AG
2023-02-01
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| author | Kende Attila Béres Fanni Szilágyi Zoltán Homonnay Zsolt Dürvanger Laura Bereczki László Trif Vladimir M. Petruševski Attila Farkas Niloofar Bayat László Kótai |
| author_facet | Kende Attila Béres Fanni Szilágyi Zoltán Homonnay Zsolt Dürvanger Laura Bereczki László Trif Vladimir M. Petruševski Attila Farkas Niloofar Bayat László Kótai |
| author_sort | Kende Attila Béres |
| collection | DOAJ |
| description | [κ<sup>2</sup>-O,O′-Carbonatotetraamminecobalt(III)] iodide, or [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>]I, named in this paper as compound <b>1,</b> was prepared and characterized comprehensively with spectroscopic (IR, Raman and UV) and single-crystal X-ray diffraction methods. Compound <b>1</b> was orthorhombic, and isomorphous with the analogous bromide. The four ammonia ligands and the carbonate anion were coordinated to the central cobalt cation in a distorted octahedral geometry. The carbonate ion formed a four-membered symmetric planar chelate ring. The complex cations were bound to each other by N-H···O hydrogen bonds and formed zigzag sheets via an extended 2D hydrogen bond network. The complex cations and iodide ions were arranged into ion pairs and each cation bound its iodide pair through three hydrogen bonds. The thermal decomposition started with the oxidation of the iodide ion by Co<sup>III</sup> in the solid phase resulting in [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>] and I<sub>2</sub>. This intermediate Co<sup>II</sup>-complex in situ decomposed into Co<sub>3</sub>O<sub>4</sub> and C-N bond containing intermediates. In inert atmosphere, CO or C-N bond containing compounds, and also, due to the in situ decomposition of CoCO<sub>3</sub> intermediate, Co<sub>3</sub>O<sub>4</sub> was formed. The quasi-intramolecular solid-phase redox reaction of [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>] might have resulted in the formation of C-N bond containing compounds with substoichiometric release of ammonia and CO<sub>2</sub> from compound <b>1</b>. The C-N bond containing intermediates reduced Co<sub>3</sub>O<sub>4</sub> into CoO and Co, whereas in oxygen-containing atmosphere, the end-product was Co<sub>3</sub>O<sub>4</sub>, even at 200 °C, and the endothermic ligand loss reaction coincided with the consecutive exothermic oxidation processes. |
| first_indexed | 2024-03-11T08:39:42Z |
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| id | doaj.art-700906ce5c284c2d9180fbb44ed7d189 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-11T08:39:42Z |
| publishDate | 2023-02-01 |
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| series | Inorganics |
| spelling | doaj.art-700906ce5c284c2d9180fbb44ed7d1892023-11-16T21:13:29ZengMDPI AGInorganics2304-67402023-02-011126810.3390/inorganics11020068Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox ReactionsKende Attila Béres0Fanni Szilágyi1Zoltán Homonnay2Zsolt Dürvanger3Laura Bereczki4László Trif5Vladimir M. Petruševski6Attila Farkas7Niloofar Bayat8László Kótai9Research Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, 1117 Budapest, HungaryProduction Division (BAY-PROD), Bay Zoltan Ltd. for Applied Research, 1 Kondorfa, 1116 Budapest, HungaryGyörgy Hevesy PhD School of Chemistry, Institute of Chemistry, ELTE Eötvös Loránd University, Pázmány Péter s. 1/A, 1117 Budapest, HungaryELKH-ELTE Protein Modelling Research Group, Pázmány Péter s. 1/A, 1117 Budapest, HungaryResearch Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, 1117 Budapest, HungaryResearch Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, 1117 Budapest, HungaryFaculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, 1000 Skopje, North MacedoniaDepartment of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, HungaryResearch Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, 1117 Budapest, HungaryResearch Centre for Natural Sciences, Institute of Materials and Environmental Chemistry, Magyar Tudósok krt. 2, 1117 Budapest, Hungary[κ<sup>2</sup>-O,O′-Carbonatotetraamminecobalt(III)] iodide, or [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>]I, named in this paper as compound <b>1,</b> was prepared and characterized comprehensively with spectroscopic (IR, Raman and UV) and single-crystal X-ray diffraction methods. Compound <b>1</b> was orthorhombic, and isomorphous with the analogous bromide. The four ammonia ligands and the carbonate anion were coordinated to the central cobalt cation in a distorted octahedral geometry. The carbonate ion formed a four-membered symmetric planar chelate ring. The complex cations were bound to each other by N-H···O hydrogen bonds and formed zigzag sheets via an extended 2D hydrogen bond network. The complex cations and iodide ions were arranged into ion pairs and each cation bound its iodide pair through three hydrogen bonds. The thermal decomposition started with the oxidation of the iodide ion by Co<sup>III</sup> in the solid phase resulting in [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>] and I<sub>2</sub>. This intermediate Co<sup>II</sup>-complex in situ decomposed into Co<sub>3</sub>O<sub>4</sub> and C-N bond containing intermediates. In inert atmosphere, CO or C-N bond containing compounds, and also, due to the in situ decomposition of CoCO<sub>3</sub> intermediate, Co<sub>3</sub>O<sub>4</sub> was formed. The quasi-intramolecular solid-phase redox reaction of [Co(NH<sub>3</sub>)<sub>4</sub>CO<sub>3</sub>] might have resulted in the formation of C-N bond containing compounds with substoichiometric release of ammonia and CO<sub>2</sub> from compound <b>1</b>. The C-N bond containing intermediates reduced Co<sub>3</sub>O<sub>4</sub> into CoO and Co, whereas in oxygen-containing atmosphere, the end-product was Co<sub>3</sub>O<sub>4</sub>, even at 200 °C, and the endothermic ligand loss reaction coincided with the consecutive exothermic oxidation processes.https://www.mdpi.com/2304-6740/11/2/68amminecarbonatecoordinationspectroscopythermal analysiscrystal structure |
| spellingShingle | Kende Attila Béres Fanni Szilágyi Zoltán Homonnay Zsolt Dürvanger Laura Bereczki László Trif Vladimir M. Petruševski Attila Farkas Niloofar Bayat László Kótai Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions Inorganics ammine carbonate coordination spectroscopy thermal analysis crystal structure |
| title | Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions |
| title_full | Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions |
| title_fullStr | Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions |
| title_full_unstemmed | Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions |
| title_short | Structural, Spectroscopic, and Thermal Decomposition Features of [Carbonatotetraamminecobalt(III)] Iodide—Insight into the Simultaneous Solid-Phase Quasi-Intramolecular Redox Reactions |
| title_sort | structural spectroscopic and thermal decomposition features of carbonatotetraamminecobalt iii iodide insight into the simultaneous solid phase quasi intramolecular redox reactions |
| topic | ammine carbonate coordination spectroscopy thermal analysis crystal structure |
| url | https://www.mdpi.com/2304-6740/11/2/68 |
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