Issue 5, 2017

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

Abstract

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Feb 2017
Accepted
07 Mar 2017
First published
07 Mar 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 3843-3851

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

J. A. Varela, S. A. Vázquez and E. Martínez-Núñez, Chem. Sci., 2017, 8, 3843 DOI: 10.1039/C7SC00549K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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