Synthesis, Spectral and Electrochemical Studies of Vanadyl β-Substituted Porphyrins and Use as a Catalyst for Olefin Epoxidation and Oxidative Bromination in Aqueous Medium
Oxidovanadium β-nitro 5,10,15,20-tetraphenylporphyrinato, VOTPPNO2 (1a) and oxidovanadium β-nitro 12,13- dibromo 5,10,15,20-tetraphenylporphyrinato, VOTPPBr2NO2 (2a) were designed and synthesized in good yield. All of the synthesized oxidovanadium porphyrins were characterized by various spectroscopic techniques viz. UV-visible, FT-IR, EPR spectroscopy and MALDI-TOF mass spectrometry, cyclic voltammetry and computational studies. In TGA study, both oxidovanadium porphyrins 1a and 2a show good thermal stability up to 277 ºC and 303 ºC respectively. The paramagnetic nature of vanadium of 1a and 2a were confirmed by electron paramagnetic resonance spectroscopy. The HOMO-LUMO gaps of 1a and 2a show less than VOTPP confirmed by cyclic voltammetry studies. In DFT studies, vanadyl porphyrin 2a slightly exhibited nonlinearity as compared to 1a due to presence of bromo groups on the porphyrin core. Oxidovanadium porphyrin catalysts, 1a and 2a were investigated for selective epoxidation of various alkenes using H2O2 as an oxidant and NaHCO3 as promotor in CH3CN at 60 ℃ with good TOF values (6159-8746 h-1). Both the catalysts mimic vanadium bromoperoxidase activity for oxidative bromination of thymol and some other phenols using HClO4-KBr-H2O2 system in water at room temperature with good TOF values (22899-35357 h-1). 1a and 2a were recovered at the end of the various catalytic cycle indicating their reusable and sustainability..
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Preprint| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
chemRxiv.org - (2024) vom: 26. März Zur Gesamtaufnahme - year:2024 |
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| Sprache: |
Englisch |
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| Beteiligte Personen: |
KUMAR, SANDEEP [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| doi: |
10.26434/chemrxiv-2024-2hlwn |
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| PPN (Katalog-ID): |
XCH043058191 |
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| 100 | 1 | |a KUMAR, SANDEEP |e verfasserin |0 (orcid)0009-0005-7545-2508 |4 aut | |
| 245 | 1 | 0 | |a Synthesis, Spectral and Electrochemical Studies of Vanadyl β-Substituted Porphyrins and Use as a Catalyst for Olefin Epoxidation and Oxidative Bromination in Aqueous Medium |
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| 520 | |a Oxidovanadium β-nitro 5,10,15,20-tetraphenylporphyrinato, VOTPPNO2 (1a) and oxidovanadium β-nitro 12,13- dibromo 5,10,15,20-tetraphenylporphyrinato, VOTPPBr2NO2 (2a) were designed and synthesized in good yield. All of the synthesized oxidovanadium porphyrins were characterized by various spectroscopic techniques viz. UV-visible, FT-IR, EPR spectroscopy and MALDI-TOF mass spectrometry, cyclic voltammetry and computational studies. In TGA study, both oxidovanadium porphyrins 1a and 2a show good thermal stability up to 277 ºC and 303 ºC respectively. The paramagnetic nature of vanadium of 1a and 2a were confirmed by electron paramagnetic resonance spectroscopy. The HOMO-LUMO gaps of 1a and 2a show less than VOTPP confirmed by cyclic voltammetry studies. In DFT studies, vanadyl porphyrin 2a slightly exhibited nonlinearity as compared to 1a due to presence of bromo groups on the porphyrin core. Oxidovanadium porphyrin catalysts, 1a and 2a were investigated for selective epoxidation of various alkenes using H2O2 as an oxidant and NaHCO3 as promotor in CH3CN at 60 ℃ with good TOF values (6159-8746 h-1). Both the catalysts mimic vanadium bromoperoxidase activity for oxidative bromination of thymol and some other phenols using HClO4-KBr-H2O2 system in water at room temperature with good TOF values (22899-35357 h-1). 1a and 2a were recovered at the end of the various catalytic cycle indicating their reusable and sustainability. | ||
| 650 | 4 | |a Chemistry |7 (dpeaa)DE-84 | |
| 650 | 4 | |a 540 |7 (dpeaa)DE-84 | |
| 700 | 1 | |a Maurya, Shailendra Kumar |4 aut | |
| 700 | 1 | |a Maurya, Mannar R. |4 aut | |
| 700 | 1 | |a Sankar, Muniappan |4 aut | |
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