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...

Descripción completa

Detalles Bibliográficos
Autores principales: De Jesus Silva, Jordan, Ferreira, Marco A. B., Fedorov, Alexey, Sigman, Matthew S., Copéret, Christophe
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