Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties
A new monoiminoacenaphthenone 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-mian (complex <b>2</b>) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(I...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/18/5706 |
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doaj-db7b551a53e342b184e032ca3ccd8678 |
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| record_format |
Article |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Anton N. Lukoyanov Iakov S. Fomenko Marko I. Gongola Lidia S. Shul’pina Nikolay S. Ikonnikov Georgiy B. Shul’pin Sergey Y. Ketkov Georgy K. Fukin Roman V. Rumyantcev Alexander S. Novikov Vladimir A. Nadolinny Maxim N. Sokolov Artem L. Gushchin |
| spellingShingle |
Anton N. Lukoyanov Iakov S. Fomenko Marko I. Gongola Lidia S. Shul’pina Nikolay S. Ikonnikov Georgiy B. Shul’pin Sergey Y. Ketkov Georgy K. Fukin Roman V. Rumyantcev Alexander S. Novikov Vladimir A. Nadolinny Maxim N. Sokolov Artem L. Gushchin Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties Molecules oxidovanadium(IV) redox-active ligands monoiminoacenaphthenone acenaphthene-1,2-diimine crystal structure cyclic voltammetry |
| author_facet |
Anton N. Lukoyanov Iakov S. Fomenko Marko I. Gongola Lidia S. Shul’pina Nikolay S. Ikonnikov Georgiy B. Shul’pin Sergey Y. Ketkov Georgy K. Fukin Roman V. Rumyantcev Alexander S. Novikov Vladimir A. Nadolinny Maxim N. Sokolov Artem L. Gushchin |
| author_sort |
Anton N. Lukoyanov |
| title |
Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties |
| title_short |
Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties |
| title_full |
Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties |
| title_fullStr |
Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties |
| title_full_unstemmed |
Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties |
| title_sort |
novel oxidovanadium complexes with redox-active r-mian and r-bian ligands: synthesis, structure, redox and catalytic properties |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2021-09-01 |
| description |
A new monoiminoacenaphthenone 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-mian (complex <b>2</b>) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl<sub>2</sub>(dpp-mian)(CH<sub>3</sub>CN)] (<b>3</b>) and [VOCl(3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian)(H<sub>2</sub>O)][VOCl<sub>3</sub>(3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian)]·2.85DME (<b>4</b>) from [VOCl<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>(H<sub>2</sub>O)] (<b>1</b>) or [VCl<sub>3</sub>(THF)<sub>3</sub>]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex <b>4</b> has an unexpected structure. Firstly, it contains 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian instead of 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-mian. Secondly, it has a binuclear structure, in contrast to <b>3</b>, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures <b>2</b> and <b>3</b>, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36–3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes <b>3</b> and <b>4</b> has been proven by EPR spectroscopy. Complexes <b>3</b> and <b>4</b> exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex <b>3</b>) and 27% (complex <b>4</b>). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh<sub>3</sub>). According to the DFT calculations, the difference in the catalytic activity of <b>3</b> and <b>4</b> is most likely associated with a different mechanism for the generation of <sup>●</sup>OH radicals. For complex <b>4</b> with electron-withdrawing CF<sub>3</sub> substituents at the diimine ligand, an alternative mechanism, different from Fenton’s and involving a redox-active ligand, is assumed. |
| topic |
oxidovanadium(IV) redox-active ligands monoiminoacenaphthenone acenaphthene-1,2-diimine crystal structure cyclic voltammetry |
| url |
https://www.mdpi.com/1420-3049/26/18/5706 |
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doaj-db7b551a53e342b184e032ca3ccd86782021-09-26T00:47:18ZengMDPI AGMolecules1420-30492021-09-01265706570610.3390/molecules26185706Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic PropertiesAnton N. Lukoyanov0Iakov S. Fomenko1Marko I. Gongola2Lidia S. Shul’pina3Nikolay S. Ikonnikov4Georgiy B. Shul’pin5Sergey Y. Ketkov6Georgy K. Fukin7Roman V. Rumyantcev8Alexander S. Novikov9Vladimir A. Nadolinny10Maxim N. Sokolov11Artem L. Gushchin12Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, RussiaNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, RussiaNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, 119991 Moscow, RussiaNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, 119991 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina 4, 119991 Moscow, RussiaRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, RussiaRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, RussiaRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, RussiaInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7/9, 199034 Saint Petersburg, RussiaNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, RussiaA new monoiminoacenaphthenone 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-mian (complex <b>2</b>) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl<sub>2</sub>(dpp-mian)(CH<sub>3</sub>CN)] (<b>3</b>) and [VOCl(3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian)(H<sub>2</sub>O)][VOCl<sub>3</sub>(3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian)]·2.85DME (<b>4</b>) from [VOCl<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>(H<sub>2</sub>O)] (<b>1</b>) or [VCl<sub>3</sub>(THF)<sub>3</sub>]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex <b>4</b> has an unexpected structure. Firstly, it contains 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-bian instead of 3,5-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>-mian. Secondly, it has a binuclear structure, in contrast to <b>3</b>, in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures <b>2</b> and <b>3</b>, non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36–3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes <b>3</b> and <b>4</b> has been proven by EPR spectroscopy. Complexes <b>3</b> and <b>4</b> exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex <b>3</b>) and 27% (complex <b>4</b>). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh<sub>3</sub>). According to the DFT calculations, the difference in the catalytic activity of <b>3</b> and <b>4</b> is most likely associated with a different mechanism for the generation of <sup>●</sup>OH radicals. For complex <b>4</b> with electron-withdrawing CF<sub>3</sub> substituents at the diimine ligand, an alternative mechanism, different from Fenton’s and involving a redox-active ligand, is assumed.https://www.mdpi.com/1420-3049/26/18/5706oxidovanadium(IV)redox-active ligandsmonoiminoacenaphthenoneacenaphthene-1,2-diiminecrystal structurecyclic voltammetry |