Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling
The mononuclear zinc(II) complex <i>cis</i>-[ZnL<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>1</b>; L = 4-(pyridin-3-ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of <b>1</b> in a mixture of DMF-H...
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MDPI AG
2020-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/11/2644 |
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| author | Anup Paul Luísa M. D. R. S. Martins Anirban Karmakar Maxim L. Kuznetsov M. Fátima C. Guedes da Silva Armando J. L. Pombeiro |
| author_facet | Anup Paul Luísa M. D. R. S. Martins Anirban Karmakar Maxim L. Kuznetsov M. Fátima C. Guedes da Silva Armando J. L. Pombeiro |
| author_sort | Anup Paul |
| collection | DOAJ |
| description | The mononuclear zinc(II) complex <i>cis</i>-[ZnL<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>1</b>; L = 4-(pyridin-3-ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of <b>1</b> in a mixture of DMF-H<sub>2</sub>O solution containing a slight excess of Cu(NO<sub>3</sub>)<sub>2</sub> × 3H<sub>2</sub>O a transmetalation reaction occurred affording the related copper(II) complex <i>trans</i>-[CuL<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>). The structures of the compounds were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism, an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties. H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks. The transmetalation was confirmed by SEM–EDS analysis. Moreover, the thermodynamic feasibility of the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities of <b>1</b> and <b>2</b> for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were investigated. The copper(II) compound <b>2</b> acts as heterogeneous catalyst for the microwave-assisted oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99%) benzaldehyde up to 66% of conversion and with a turnover frequency (TOF) of 132 h<sup>−1</sup>. The zinc(II) complex <b>1</b> is the most active catalyst (up to 87% yield) towards the nitroaldol (Henry) coupling reaction between benzaldehyde and nitro-methane or -ethane to afford the corresponding β-nitro alcohols. The reaction of benzaldehyde with nitroethane in the presence of <b>1</b> produced 2-nitro-1-phenylpropanol in the <i>syn</i> and the <i>anti</i> diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34). |
| first_indexed | 2024-03-10T19:19:34Z |
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| last_indexed | 2024-03-10T19:19:34Z |
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| spelling | doaj.art-1e1e55d521374b0b910d5a46ee24083d2023-11-20T03:04:52ZengMDPI AGMolecules1420-30492020-06-012511264410.3390/molecules25112644Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol CouplingAnup Paul0Luísa M. D. R. S. Martins1Anirban Karmakar2Maxim L. Kuznetsov3M. Fátima C. Guedes da Silva4Armando J. L. Pombeiro5Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, PortugalThe mononuclear zinc(II) complex <i>cis</i>-[ZnL<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>1</b>; L = 4-(pyridin-3-ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of <b>1</b> in a mixture of DMF-H<sub>2</sub>O solution containing a slight excess of Cu(NO<sub>3</sub>)<sub>2</sub> × 3H<sub>2</sub>O a transmetalation reaction occurred affording the related copper(II) complex <i>trans</i>-[CuL<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>). The structures of the compounds were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism, an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties. H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks. The transmetalation was confirmed by SEM–EDS analysis. Moreover, the thermodynamic feasibility of the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities of <b>1</b> and <b>2</b> for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were investigated. The copper(II) compound <b>2</b> acts as heterogeneous catalyst for the microwave-assisted oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99%) benzaldehyde up to 66% of conversion and with a turnover frequency (TOF) of 132 h<sup>−1</sup>. The zinc(II) complex <b>1</b> is the most active catalyst (up to 87% yield) towards the nitroaldol (Henry) coupling reaction between benzaldehyde and nitro-methane or -ethane to afford the corresponding β-nitro alcohols. The reaction of benzaldehyde with nitroethane in the presence of <b>1</b> produced 2-nitro-1-phenylpropanol in the <i>syn</i> and the <i>anti</i> diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34).https://www.mdpi.com/1420-3049/25/11/2644amide functionalizedtransmetalationDFT calculationsoxidation of styrenenitroaldol |
| spellingShingle | Anup Paul Luísa M. D. R. S. Martins Anirban Karmakar Maxim L. Kuznetsov M. Fátima C. Guedes da Silva Armando J. L. Pombeiro Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling Molecules amide functionalized transmetalation DFT calculations oxidation of styrene nitroaldol |
| title | Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling |
| title_full | Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling |
| title_fullStr | Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling |
| title_full_unstemmed | Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling |
| title_short | Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling |
| title_sort | zn ii to cu ii transmetalation in an amide functionalized complex and catalytic applications in styrene oxidation and nitroaldol coupling |
| topic | amide functionalized transmetalation DFT calculations oxidation of styrene nitroaldol |
| url | https://www.mdpi.com/1420-3049/25/11/2644 |
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