Cargando…
Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation
Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on cata...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6540189/ https://www.ncbi.nlm.nih.gov/pubmed/31083594 http://dx.doi.org/10.3390/molecules24091823 |
_version_ | 1783422563566747648 |
---|---|
author | Strekalova, Sofia Khrizanforov, Mikhail Budnikova, Yulia |
author_facet | Strekalova, Sofia Khrizanforov, Mikhail Budnikova, Yulia |
author_sort | Strekalova, Sofia |
collection | PubMed |
description | Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on catalytic current growth of oxidation or reduction of the metal catalysts (Co(II), Mn(II), Ni(II), Mn(II)/Ni(II), Mn(II)/Co(II), and Co(II)/Ni(II)), quantitative characteristics of the regeneration of catalysts were determined, for example, for Mn(II), Ni(II) and Mn(II)/Ni(II), Co(II)/Ni(II) pairs. Calculations confirmed the previously made synthetic observations on the synergistic effect of certain metal ions in binary catalytic systems (Mn(II)bpy/Ni(II)bpy and Ni(II)bpy/Co(II)bpy); for mixtures, the observed rate constants, or TOF, were 690 s(−1) and 721 s(−1), respectively, and product yields were higher for monometallic catalytic systems (up to 71% for bimetallic catalytic systems and ~30% for monometallic catalytic systems). In some cases, the appearance of pre-waves after adding H-phosphonates confirmed the preceding chemical reaction. It also confirmed the formation of metal phosphonates in the time scale of voltammetry, oxidizing or reducing at lower potentials than the original (RO)(2)P(O)H and metal complex, which could be used for fast diagnostics of metal ion and dialkyl-H-phosphonate interactions. Electrochemical transfer of an electron to (from) metal phosphonate generates a phosphonyl radical, which can then react with different arenes to give the products of aromatic C–H phosphonation. |
format | Online Article Text |
id | pubmed-6540189 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-65401892019-05-31 Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation Strekalova, Sofia Khrizanforov, Mikhail Budnikova, Yulia Molecules Article Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C–H phosphonation in the presence of a phosphorus precursor, for example, dialkyl-H-phosphonate. Based on catalytic current growth of oxidation or reduction of the metal catalysts (Co(II), Mn(II), Ni(II), Mn(II)/Ni(II), Mn(II)/Co(II), and Co(II)/Ni(II)), quantitative characteristics of the regeneration of catalysts were determined, for example, for Mn(II), Ni(II) and Mn(II)/Ni(II), Co(II)/Ni(II) pairs. Calculations confirmed the previously made synthetic observations on the synergistic effect of certain metal ions in binary catalytic systems (Mn(II)bpy/Ni(II)bpy and Ni(II)bpy/Co(II)bpy); for mixtures, the observed rate constants, or TOF, were 690 s(−1) and 721 s(−1), respectively, and product yields were higher for monometallic catalytic systems (up to 71% for bimetallic catalytic systems and ~30% for monometallic catalytic systems). In some cases, the appearance of pre-waves after adding H-phosphonates confirmed the preceding chemical reaction. It also confirmed the formation of metal phosphonates in the time scale of voltammetry, oxidizing or reducing at lower potentials than the original (RO)(2)P(O)H and metal complex, which could be used for fast diagnostics of metal ion and dialkyl-H-phosphonate interactions. Electrochemical transfer of an electron to (from) metal phosphonate generates a phosphonyl radical, which can then react with different arenes to give the products of aromatic C–H phosphonation. MDPI 2019-05-11 /pmc/articles/PMC6540189/ /pubmed/31083594 http://dx.doi.org/10.3390/molecules24091823 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Strekalova, Sofia Khrizanforov, Mikhail Budnikova, Yulia Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title | Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title_full | Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title_fullStr | Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title_full_unstemmed | Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title_short | Evaluation of Transition Metal Catalysts in Electrochemically Induced Aromatic Phosphonation |
title_sort | evaluation of transition metal catalysts in electrochemically induced aromatic phosphonation |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6540189/ https://www.ncbi.nlm.nih.gov/pubmed/31083594 http://dx.doi.org/10.3390/molecules24091823 |
work_keys_str_mv | AT strekalovasofia evaluationoftransitionmetalcatalystsinelectrochemicallyinducedaromaticphosphonation AT khrizanforovmikhail evaluationoftransitionmetalcatalystsinelectrochemicallyinducedaromaticphosphonation AT budnikovayulia evaluationoftransitionmetalcatalystsinelectrochemicallyinducedaromaticphosphonation |