Cargando…
Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
A combination of high-throughput experimentation (HTE), surface organometallic chemistry (SOMC) and statistical data analysis provided the platform to analyze in situ silica-grafted Mo imido alkylidene catalysts based on a library of 35 phenols. Overall, these tools allowed for the identification of...
Autores principales: | , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2020
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7553044/ https://www.ncbi.nlm.nih.gov/pubmed/33133485 http://dx.doi.org/10.1039/d0sc02594a |
_version_ | 1783593523809878016 |
---|---|
author | De Jesus Silva, Jordan Ferreira, Marco A. B. Fedorov, Alexey Sigman, Matthew S. Copéret, Christophe |
author_facet | De Jesus Silva, Jordan Ferreira, Marco A. B. Fedorov, Alexey Sigman, Matthew S. Copéret, Christophe |
author_sort | De Jesus Silva, Jordan |
collection | PubMed |
description | A combination of high-throughput experimentation (HTE), surface organometallic chemistry (SOMC) and statistical data analysis provided the platform to analyze in situ silica-grafted Mo imido alkylidene catalysts based on a library of 35 phenols. Overall, these tools allowed for the identification of σ-donor electronic effects and dispersive interactions and as key drivers in a prototypical metathesis reaction, homodimerization of 1-nonene. Univariate and multivariate correlation analysis confirmed the categorization of the catalytic data into two groups, depending on the presence of aryl groups in ortho position of the phenol ligand. The initial activity (TOF(in)) was predominantly correlated to the σ-donor ability of the aryloxy ligands, while the overall catalytic performance (TON(1 h)) was mainly dependent on attractive dispersive interactions with the used phenol ligands featuring aryl ortho substituents and, in sharp contrast, repulsive dispersive interactions with phenol free of aryl ortho substituents. This work outlines a fast and efficient workflow of gaining molecular-level insight into supported metathesis catalysts and highlights σ-donor ability and noncovalent interactions as crucial properties for designing active d(0) supported metathesis catalysts. |
format | Online Article Text |
id | pubmed-7553044 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-75530442020-10-30 Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis De Jesus Silva, Jordan Ferreira, Marco A. B. Fedorov, Alexey Sigman, Matthew S. Copéret, Christophe Chem Sci Chemistry A combination of high-throughput experimentation (HTE), surface organometallic chemistry (SOMC) and statistical data analysis provided the platform to analyze in situ silica-grafted Mo imido alkylidene catalysts based on a library of 35 phenols. Overall, these tools allowed for the identification of σ-donor electronic effects and dispersive interactions and as key drivers in a prototypical metathesis reaction, homodimerization of 1-nonene. Univariate and multivariate correlation analysis confirmed the categorization of the catalytic data into two groups, depending on the presence of aryl groups in ortho position of the phenol ligand. The initial activity (TOF(in)) was predominantly correlated to the σ-donor ability of the aryloxy ligands, while the overall catalytic performance (TON(1 h)) was mainly dependent on attractive dispersive interactions with the used phenol ligands featuring aryl ortho substituents and, in sharp contrast, repulsive dispersive interactions with phenol free of aryl ortho substituents. This work outlines a fast and efficient workflow of gaining molecular-level insight into supported metathesis catalysts and highlights σ-donor ability and noncovalent interactions as crucial properties for designing active d(0) supported metathesis catalysts. Royal Society of Chemistry 2020-06-10 /pmc/articles/PMC7553044/ /pubmed/33133485 http://dx.doi.org/10.1039/d0sc02594a Text en This journal is © The Royal Society of Chemistry 2020 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry De Jesus Silva, Jordan Ferreira, Marco A. B. Fedorov, Alexey Sigman, Matthew S. Copéret, Christophe Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis |
title | Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
|
title_full | Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
|
title_fullStr | Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
|
title_full_unstemmed | Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
|
title_short | Molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis
|
title_sort | molecular-level insight in supported olefin metathesis catalysts by combining surface organometallic chemistry, high throughput experimentation, and data analysis |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7553044/ https://www.ncbi.nlm.nih.gov/pubmed/33133485 http://dx.doi.org/10.1039/d0sc02594a |
work_keys_str_mv | AT dejesussilvajordan molecularlevelinsightinsupportedolefinmetathesiscatalystsbycombiningsurfaceorganometallicchemistryhighthroughputexperimentationanddataanalysis AT ferreiramarcoab molecularlevelinsightinsupportedolefinmetathesiscatalystsbycombiningsurfaceorganometallicchemistryhighthroughputexperimentationanddataanalysis AT fedorovalexey molecularlevelinsightinsupportedolefinmetathesiscatalystsbycombiningsurfaceorganometallicchemistryhighthroughputexperimentationanddataanalysis AT sigmanmatthews molecularlevelinsightinsupportedolefinmetathesiscatalystsbycombiningsurfaceorganometallicchemistryhighthroughputexperimentationanddataanalysis AT coperetchristophe molecularlevelinsightinsupportedolefinmetathesiscatalystsbycombiningsurfaceorganometallicchemistryhighthroughputexperimentationanddataanalysis |