Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes
Dinuclear di-<i>µ</i>-oxo complexes of Mn<sup>3+</sup> and Mn<sup>4+</sup> ions, and mononuclear complexes of Mn<sup>3+</sup> ions with tetraazamacrocycles ([12]aneN<sub>4</sub>, [14]aneN<sub>4</sub>, [15]aneN<sub>4</su...
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| author | Danuta Tomczyk Sławomira Skrzypek Piotr Seliger |
| author_facet | Danuta Tomczyk Sławomira Skrzypek Piotr Seliger |
| author_sort | Danuta Tomczyk |
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| description | Dinuclear di-<i>µ</i>-oxo complexes of Mn<sup>3+</sup> and Mn<sup>4+</sup> ions, and mononuclear complexes of Mn<sup>3+</sup> ions with tetraazamacrocycles ([12]aneN<sub>4</sub>, [14]aneN<sub>4</sub>, [15]aneN<sub>4</sub>) and <i>C</i>-substituted derivative (Me<sub>6</sub>[14]aneN<sub>4</sub>) as well as mononuclear complexes of Mn<sup>2+</sup> ions with <i>N</i>-substituted derivatives ((<i>N</i>-Me)<sub>2</sub>[14]aneN<sub>4</sub>, (<i>N</i>-Me)<sub>4</sub>[14]aneN<sub>4</sub>, (<i>N</i>-Me)Me<sub>2</sub>py [14]aneN<sub>4</sub>) and with oxo<sub>2</sub>[14]aneN<sub>4</sub> were studied. Based on spectroscopic (UV VIS and IR) and conductometric studies, the types of synthesised complexes (<i>cis</i> or <i>trans</i> isomers of mononuclear Mn<sup>3+</sup> complexes, oxygen bridges and class II according to Robin and Day classification for dinuclear complexes) were determined. On the basis of voltammetric and spectroelectrochemical studies, <i>trans-cis</i> isomerisation at the level of Mn<sup>2+</sup> ion complexes and <i>cis-trans</i> isomerisation at the level of Mn<sup>3+</sup> ion complexes were demonstrated for complexes of ligands with free C positions. The <i>N</i>-substituted derivatives oxidise according to the EC mechanism, in which the follow-up reaction is a disproportionation reaction. The thermodynamic stabilisation of Mn<sup>3+</sup> ions was determined by comparing the formal potentials (<i>E<sub>f</sub></i><sup>0</sup>), the disproportionation constants (<i>k</i><sub>1</sub>) and the formation constants (<i>β<sup>III</sup></i>). The study showed the possibility of oxidation of mononuclear, pseudo-octahedral Mn<sup>3+</sup> ion complexes to dinuclear complexes and the greatest stabilisation of Mn<sup>3+</sup> ions, both in monomers and dimers of ligands with free <i>N</i> positions. |
| format | Article |
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| institution | DOAJ |
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| publishDate | 2025-04-01 |
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| spelling | doaj-art-87ea4a90a1514bf09b191d46dc8452e32025-08-20T03:13:58ZengMDPI AGMolecules1420-30492025-04-01308186010.3390/molecules30081860Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode ProcessesDanuta Tomczyk0Sławomira Skrzypek1Piotr Seliger2University of Lodz, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Tamka 12, 91-403 Lodz, PolandUniversity of Lodz, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Tamka 12, 91-403 Lodz, PolandUniversity of Lodz, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Tamka 12, 91-403 Lodz, PolandDinuclear di-<i>µ</i>-oxo complexes of Mn<sup>3+</sup> and Mn<sup>4+</sup> ions, and mononuclear complexes of Mn<sup>3+</sup> ions with tetraazamacrocycles ([12]aneN<sub>4</sub>, [14]aneN<sub>4</sub>, [15]aneN<sub>4</sub>) and <i>C</i>-substituted derivative (Me<sub>6</sub>[14]aneN<sub>4</sub>) as well as mononuclear complexes of Mn<sup>2+</sup> ions with <i>N</i>-substituted derivatives ((<i>N</i>-Me)<sub>2</sub>[14]aneN<sub>4</sub>, (<i>N</i>-Me)<sub>4</sub>[14]aneN<sub>4</sub>, (<i>N</i>-Me)Me<sub>2</sub>py [14]aneN<sub>4</sub>) and with oxo<sub>2</sub>[14]aneN<sub>4</sub> were studied. Based on spectroscopic (UV VIS and IR) and conductometric studies, the types of synthesised complexes (<i>cis</i> or <i>trans</i> isomers of mononuclear Mn<sup>3+</sup> complexes, oxygen bridges and class II according to Robin and Day classification for dinuclear complexes) were determined. On the basis of voltammetric and spectroelectrochemical studies, <i>trans-cis</i> isomerisation at the level of Mn<sup>2+</sup> ion complexes and <i>cis-trans</i> isomerisation at the level of Mn<sup>3+</sup> ion complexes were demonstrated for complexes of ligands with free C positions. The <i>N</i>-substituted derivatives oxidise according to the EC mechanism, in which the follow-up reaction is a disproportionation reaction. The thermodynamic stabilisation of Mn<sup>3+</sup> ions was determined by comparing the formal potentials (<i>E<sub>f</sub></i><sup>0</sup>), the disproportionation constants (<i>k</i><sub>1</sub>) and the formation constants (<i>β<sup>III</sup></i>). The study showed the possibility of oxidation of mononuclear, pseudo-octahedral Mn<sup>3+</sup> ion complexes to dinuclear complexes and the greatest stabilisation of Mn<sup>3+</sup> ions, both in monomers and dimers of ligands with free <i>N</i> positions.https://www.mdpi.com/1420-3049/30/8/1860manganese dinuclear complexcyclamcyclentetraazamacrocycledisproportionation constant |
| spellingShingle | Danuta Tomczyk Sławomira Skrzypek Piotr Seliger Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes Molecules manganese dinuclear complex cyclam cyclen tetraazamacrocycle disproportionation constant |
| title | Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes |
| title_full | Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes |
| title_fullStr | Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes |
| title_full_unstemmed | Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes |
| title_short | Influence of the Type of Macrocycle on the Stabilisation of the High Oxidation State of the Manganese Ion and Electrode Processes |
| title_sort | influence of the type of macrocycle on the stabilisation of the high oxidation state of the manganese ion and electrode processes |
| topic | manganese dinuclear complex cyclam cyclen tetraazamacrocycle disproportionation constant |
| url | https://www.mdpi.com/1420-3049/30/8/1860 |
| work_keys_str_mv | AT danutatomczyk influenceofthetypeofmacrocycleonthestabilisationofthehighoxidationstateofthemanganeseionandelectrodeprocesses AT sławomiraskrzypek influenceofthetypeofmacrocycleonthestabilisationofthehighoxidationstateofthemanganeseionandelectrodeprocesses AT piotrseliger influenceofthetypeofmacrocycleonthestabilisationofthehighoxidationstateofthemanganeseionandelectrodeprocesses |