Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand
Chiral metal-templated complexes are attractive catalysts for organic synthetic transformations. Herein, we introduce a novel chiral cobalt(III)-templated complex based on chiral <i>trans</i>-3,4-diamino-1-benzylpyrrolidine and 3,5-di-<i>tert</i>-butyl-salicylaldehyde which f...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-01-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/11/2/152 |
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| author | Tat’yana F. Savel’yeva Olga V. Khromova Vladimir A. Larionov Alexander F. Smol’yakov Ivan V. Fedyanin Yuri N. Belokon Victor I. Maleev |
| author_facet | Tat’yana F. Savel’yeva Olga V. Khromova Vladimir A. Larionov Alexander F. Smol’yakov Ivan V. Fedyanin Yuri N. Belokon Victor I. Maleev |
| author_sort | Tat’yana F. Savel’yeva |
| collection | DOAJ |
| description | Chiral metal-templated complexes are attractive catalysts for organic synthetic transformations. Herein, we introduce a novel chiral cobalt(III)-templated complex based on chiral <i>trans</i>-3,4-diamino-1-benzylpyrrolidine and 3,5-di-<i>tert</i>-butyl-salicylaldehyde which features both hydrogen bond donor and Brønsted base functionalities. The obtained complexes were fully characterized by <sup>1</sup>H, <sup>13</sup>C NMR, IR-, UV-vis, CD-spectroscopy and by a single X-ray diffraction analysis. It was shown that chlorine anion is connected with amino groups of the complex via a hydrogen bonding. DFT calculations of charges and molecular electrostatic potential of the cobalt(III) complex showed that the basicity of the complex is certainly diminished as compared with the routine tertiary amines but the acidity of the conjugated acid of the complex should be increased. Thus, the catalytic potential of the complex may be much greater as a chiral acid than a chiral base. We believe that this work opens a new way in chiral bifunctional catalyst design. |
| first_indexed | 2024-03-09T04:04:33Z |
| format | Article |
| id | doaj.art-655361f1bac5423e8e4e82c7627341f6 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-09T04:04:33Z |
| publishDate | 2021-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-655361f1bac5423e8e4e82c7627341f62023-12-03T14:08:46ZengMDPI AGCatalysts2073-43442021-01-0111215210.3390/catal11020152Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the LigandTat’yana F. Savel’yeva0Olga V. Khromova1Vladimir A. Larionov2Alexander F. Smol’yakov3Ivan V. Fedyanin4Yuri N. Belokon5Victor I. Maleev6A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, RussiaChiral metal-templated complexes are attractive catalysts for organic synthetic transformations. Herein, we introduce a novel chiral cobalt(III)-templated complex based on chiral <i>trans</i>-3,4-diamino-1-benzylpyrrolidine and 3,5-di-<i>tert</i>-butyl-salicylaldehyde which features both hydrogen bond donor and Brønsted base functionalities. The obtained complexes were fully characterized by <sup>1</sup>H, <sup>13</sup>C NMR, IR-, UV-vis, CD-spectroscopy and by a single X-ray diffraction analysis. It was shown that chlorine anion is connected with amino groups of the complex via a hydrogen bonding. DFT calculations of charges and molecular electrostatic potential of the cobalt(III) complex showed that the basicity of the complex is certainly diminished as compared with the routine tertiary amines but the acidity of the conjugated acid of the complex should be increased. Thus, the catalytic potential of the complex may be much greater as a chiral acid than a chiral base. We believe that this work opens a new way in chiral bifunctional catalyst design.https://www.mdpi.com/2073-4344/11/2/152metal-templated complexchiralitychiral-at-metalcobalt(III)hydrogen bond donorSchiff base |
| spellingShingle | Tat’yana F. Savel’yeva Olga V. Khromova Vladimir A. Larionov Alexander F. Smol’yakov Ivan V. Fedyanin Yuri N. Belokon Victor I. Maleev Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand Catalysts metal-templated complex chirality chiral-at-metal cobalt(III) hydrogen bond donor Schiff base |
| title | Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand |
| title_full | Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand |
| title_fullStr | Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand |
| title_full_unstemmed | Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand |
| title_short | Expanding the Family of Octahedral Chiral-at-Metal Cobalt(III) Catalysts by Introducing Tertiary Amine Moiety into the Ligand |
| title_sort | expanding the family of octahedral chiral at metal cobalt iii catalysts by introducing tertiary amine moiety into the ligand |
| topic | metal-templated complex chirality chiral-at-metal cobalt(III) hydrogen bond donor Schiff base |
| url | https://www.mdpi.com/2073-4344/11/2/152 |
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