How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes
Thiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we s...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-03-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/11/4/149 |
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| author | Michael Papadakis Alexandre Barrozo Léa Delmotte Tatiana Straistari Sergiu Shova Marius Réglier Vera Krewald Sylvain Bertaina Renaud Hardré Maylis Orio |
| author_facet | Michael Papadakis Alexandre Barrozo Léa Delmotte Tatiana Straistari Sergiu Shova Marius Réglier Vera Krewald Sylvain Bertaina Renaud Hardré Maylis Orio |
| author_sort | Michael Papadakis |
| collection | DOAJ |
| description | Thiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we show the possibility of a new strategy, involving the nuclearity of the system, meaning the number of metal centers. We report the synthesis and characterization of a trinuclear nickel-thiocarbohydrazone complex displaying an improved turnover rate compared with its mononuclear counterpart. We use DFT calculations to show that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism found in the mononuclear complex. Finally, we show that two possible mechanisms can be assigned to this catalyst, both involving an initial double reduction of the system. |
| first_indexed | 2024-03-11T04:55:26Z |
| format | Article |
| id | doaj.art-bbbc7922f6904502910741a6be5adb2c |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-11T04:55:26Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-bbbc7922f6904502910741a6be5adb2c2023-11-17T19:45:17ZengMDPI AGInorganics2304-67402023-03-0111414910.3390/inorganics11040149How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based ComplexesMichael Papadakis0Alexandre Barrozo1Léa Delmotte2Tatiana Straistari3Sergiu Shova4Marius Réglier5Vera Krewald6Sylvain Bertaina7Renaud Hardré8Maylis Orio9Aix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceInstitute of Macromolecular Chemistry Petru Poni, 700487 Iasi, RomaniaAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceDepartment of Chemistry, Theoretical Chemistry, Technical University Darmstadt, 64289 Darmstadt, GermanyAix-Marseille Univ, CNRS, IN2MP UMR 7334, 13397 Marseille, FranceAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceAix-Marseille Univ, CNRS, Centrale Marseille, iSm2, 13397 Marseille, FranceThiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we show the possibility of a new strategy, involving the nuclearity of the system, meaning the number of metal centers. We report the synthesis and characterization of a trinuclear nickel-thiocarbohydrazone complex displaying an improved turnover rate compared with its mononuclear counterpart. We use DFT calculations to show that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism found in the mononuclear complex. Finally, we show that two possible mechanisms can be assigned to this catalyst, both involving an initial double reduction of the system.https://www.mdpi.com/2304-6740/11/4/149hydrogen evolutionbio-inspirationelectrocatalysisquantum chemistryreaction mechanism |
| spellingShingle | Michael Papadakis Alexandre Barrozo Léa Delmotte Tatiana Straistari Sergiu Shova Marius Réglier Vera Krewald Sylvain Bertaina Renaud Hardré Maylis Orio How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes Inorganics hydrogen evolution bio-inspiration electrocatalysis quantum chemistry reaction mechanism |
| title | How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes |
| title_full | How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes |
| title_fullStr | How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes |
| title_full_unstemmed | How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes |
| title_short | How Metal Nuclearity Impacts Electrocatalytic H<sub>2</sub> Production in Thiocarbohydrazone-Based Complexes |
| title_sort | how metal nuclearity impacts electrocatalytic h sub 2 sub production in thiocarbohydrazone based complexes |
| topic | hydrogen evolution bio-inspiration electrocatalysis quantum chemistry reaction mechanism |
| url | https://www.mdpi.com/2304-6740/11/4/149 |
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