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An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis

A novel computational method is proposed in this work for use in discovering reaction mechanisms and solving the kinetics of transition metal-catalyzed reactions. The method does not rely on either chemical intuition or assumed a priori mechanisms, and it works in a fully automated fashion. Its core...

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Autores principales: Varela, J. A., Vázquez, S. A., Martínez-Núñez, E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5577717/
https://www.ncbi.nlm.nih.gov/pubmed/28966776
http://dx.doi.org/10.1039/c7sc00549k
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author Varela, J. A.
Vázquez, S. A.
Martínez-Núñez, E.
author_facet Varela, J. A.
Vázquez, S. A.
Martínez-Núñez, E.
author_sort Varela, J. A.
collection PubMed
description A novel computational method is proposed in this work for use in discovering reaction mechanisms and solving the kinetics of transition metal-catalyzed reactions. The method does not rely on either chemical intuition or assumed a priori mechanisms, and it works in a fully automated fashion. Its core is a procedure, recently developed by one of the authors, that combines accelerated direct dynamics with an efficient geometry-based post-processing algorithm to find transition states (Martinez-Nunez, E., J. Comput. Chem. 2015, 36, 222–234). In the present work, several auxiliary tools have been added to deal with the specific features of transition metal catalytic reactions. As a test case, we chose the cobalt-catalyzed hydroformylation of ethylene because of its well-established mechanism, and the fact that it has already been used in previous automated computational studies. Besides the generally accepted mechanism of Heck and Breslow, several side reactions, such as hydrogenation of the alkene, emerged from our calculations. Additionally, the calculated rate law for the hydroformylation reaction agrees reasonably well with those obtained in previous experimental and theoretical studies.
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spelling pubmed-55777172017-09-29 An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis Varela, J. A. Vázquez, S. A. Martínez-Núñez, E. Chem Sci Chemistry A novel computational method is proposed in this work for use in discovering reaction mechanisms and solving the kinetics of transition metal-catalyzed reactions. The method does not rely on either chemical intuition or assumed a priori mechanisms, and it works in a fully automated fashion. Its core is a procedure, recently developed by one of the authors, that combines accelerated direct dynamics with an efficient geometry-based post-processing algorithm to find transition states (Martinez-Nunez, E., J. Comput. Chem. 2015, 36, 222–234). In the present work, several auxiliary tools have been added to deal with the specific features of transition metal catalytic reactions. As a test case, we chose the cobalt-catalyzed hydroformylation of ethylene because of its well-established mechanism, and the fact that it has already been used in previous automated computational studies. Besides the generally accepted mechanism of Heck and Breslow, several side reactions, such as hydrogenation of the alkene, emerged from our calculations. Additionally, the calculated rate law for the hydroformylation reaction agrees reasonably well with those obtained in previous experimental and theoretical studies. Royal Society of Chemistry 2017-05-01 2017-03-07 /pmc/articles/PMC5577717/ /pubmed/28966776 http://dx.doi.org/10.1039/c7sc00549k Text en This journal is © The Royal Society of Chemistry 2017 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Varela, J. A.
Vázquez, S. A.
Martínez-Núñez, E.
An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title_full An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title_fullStr An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title_full_unstemmed An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title_short An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
title_sort automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5577717/
https://www.ncbi.nlm.nih.gov/pubmed/28966776
http://dx.doi.org/10.1039/c7sc00549k
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