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Dipolar cycloadditions and the “|Δμ| big is good” rule: a computational study

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Abstract

We analyze the validity of the “|Δμ| big is good” rule over a set of different 1,3-dipolar cycloaddition reactions. We consider different factors that could be important in the practical application of this principle, chiefly: intermolecular interactions and geometry reorganization. We observe that while a simple model of the reagent–reagent perturbations suffices to describe charge transfer in these reactions, it fails when applied to the “|Δμ| big is good” rule. On the contrary, geometry changes are proven to be of paramount importance and only when they are correctly taken care of the “|Δμ| big is good” rule provides accurate predictions.

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Acknowledgements

We thank NSERC and Compute Canada for support. RAMQ acknowledges funding from York University in the form of a York Science Fellowship. Also, we would like to dedicate this work to Pratim Kumar Chattaraj, whose relentless work in C-DFT has contributed to elucidate the physical basis of many important reactivity principles.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada

    Ramón Alain Miranda-Quintana & Paul W. Ayers

  2. Department of Chemistry, York University, Toronto, ON, Canada

    Ramón Alain Miranda-Quintana

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  1. Ramón Alain Miranda-Quintana
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  2. Paul W. Ayers
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Correspondence to Ramón Alain Miranda-Quintana.

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Miranda-Quintana, R.A., Ayers, P.W. Dipolar cycloadditions and the “|Δμ| big is good” rule: a computational study. Theor Chem Acc 137, 177 (2018). https://doi.org/10.1007/s00214-018-2391-0

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