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Quantitative DFT modeling of product concentrations in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study

Abstract

DFT calculations are widely used for computing properties, reaction mechanisms and energy profiles in organometallic reactions. A qualitative agreement between the experimental and the calculated results seems to be usually enough to validate a computational methodology but recent advances in computation indicate that a nearly quantitative agreement should be possible if a proper DFT study is carried out. Final percent product concentrations, often reported as yields, are by far the most commonly reported properties in experimental homogeneous catalysis studies but those have been never reproduced with DFT methods. The recently reported stoichiometric pentafluoroethylation of benzoic acid chlorides (R-C6H4COCl) with [(phen)Cu(PPh3)C2F5] (phen = 1,10-phenanthroline, PPh3 = triphenylphosphine) has been used as a case study to check whether the experimental product concentrations can be reproduced by any of the most popular DFT approaches with high enough accuracy. To this end, the free energy profile for the pentafluoroethylation of benzoic acid chloride has been computed using 14 different DFT methods. These computed free energy profiles have been employed to build kinetic models predicting the final product concentration in solution. The best results are obtained with the D3-dispersion corrected B3LYP functional, which has been successfully used afterwards to model the reaction outcome of other simple (R = o-Me, p-Me, p-Cl, p-F, etc.) benzoic acid chlorides. The product concentrations of more complex reaction networks in which more than one position of the substrate may be activated by the copper catalyst (R = o-Br and p-I) are also predicted properly.

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Publication details

The article was received on 21 Aug 2017, accepted on 10 Oct 2017 and first published on 10 Oct 2017


Article type: Paper
DOI: 10.1039/C7CP05709A
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Quantitative DFT modeling of product concentrations in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study

    J. Jover , Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP05709A

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