Theoretical Studies of SN2 Reactions

Present review outlines the experimental and theoretical studies on the SN 2 reactions at heteroatoms ( N , O and S ) and ion pair systems in recent years, especially introduce research carried out at our group in detail. The similarities and differences between SN 2 at heteroatoms and at carbon are discussed. Some new structure–energy relationships were proposed. The accuracy of various theoretical schemes for calculating potential energy surfaces has been assessed.

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Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments"

10.26434/chemrxiv.12982358 ◽

2020 ◽

Author(s):

Anoop Thomas ◽

Lucas Lethuillier-Karl ◽

Joseph Moran ◽

Thomas Ebbesen

Keyword(s):

Reaction Mechanisms ◽

Recent Article ◽

Cavity Mode ◽

Vibrational Mode ◽

Theoretical Studies ◽

Vibrational Modes ◽

Experimental Proof ◽

Sn2 Reactions ◽

Vibrational Bands ◽

Supplementary Material

We welcome the large number of theoretical studies to analyze our experiments on chemistry under VSC. As Climent and Feist state in their recent article, many details are not understood. 1 However, there should be no need to misrepresent our results. In their paper, the authors re-analyze, not the chemistry under VSC, but the reactions that we used that have been studied for over half a century and for which there is no consensus about the details of the mechanism. 2 Secondly, they try to assign the vibrational bands of the reactants. Indeed, as they find, they are often mixed (coupled vibrational modes). For simplicity, it is commonplace in chemistry to describe vibrations according to their main contribution, a convention that we follow in our papers. Since there are differences between our results and their calculations, they assume that our assignments are wrong. Finally, they conclude that we must have coupled the solvent, apparently by a higher cavity mode, despite the experimental proof to the contrary in the original paper.3 The proof that the solvent was not coupled is reproduced below for those who are interested, together with one example of an unequivocal assignment that was in the supplementary material, 4 which Climent and Feist presumably overlooked.

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Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments"

10.26434/chemrxiv.12982358.v1 ◽

2020 ◽

Author(s):

Anoop Thomas ◽

Lucas Lethuillier-Karl ◽

Joseph Moran ◽

Thomas Ebbesen

Keyword(s):

Reaction Mechanisms ◽

Recent Article ◽

Cavity Mode ◽

Vibrational Mode ◽

Theoretical Studies ◽

Vibrational Modes ◽

Experimental Proof ◽

Sn2 Reactions ◽

Vibrational Bands ◽

Supplementary Material

We welcome the large number of theoretical studies to analyze our experiments on chemistry under VSC. As Climent and Feist state in their recent article, many details are not understood. 1 However, there should be no need to misrepresent our results. In their paper, the authors re-analyze, not the chemistry under VSC, but the reactions that we used that have been studied for over half a century and for which there is no consensus about the details of the mechanism. 2 Secondly, they try to assign the vibrational bands of the reactants. Indeed, as they find, they are often mixed (coupled vibrational modes). For simplicity, it is commonplace in chemistry to describe vibrations according to their main contribution, a convention that we follow in our papers. Since there are differences between our results and their calculations, they assume that our assignments are wrong. Finally, they conclude that we must have coupled the solvent, apparently by a higher cavity mode, despite the experimental proof to the contrary in the original paper.3 The proof that the solvent was not coupled is reproduced below for those who are interested, together with one example of an unequivocal assignment that was in the supplementary material, 4 which Climent and Feist presumably overlooked.

Download Full-text