Specificities of application of the supermolecule method to the calculation of reaction mechanisms in a protonodonor medium. Ethylene carbonate aminolysis in methanol

Specificities of application of the supermolecule method to the calculation of reaction... The specificities of application of the supermolecule method to the calculation of mechanisms of reactions in a protonodonor medium are considered using as an example the reaction of methylamine with ethylene carbonate in methanol. The energies of non-interacting solvated reactants have been used as the reference levels for calculation of relative energies. The problems that result from using the energies of the pre-reaction complexes or the sums of the energies of infinitely separated reactants as the reference levels are noted. The optimal number of the solvent molecules necessary to comprehensively model the reaction under consideration is found. Two possibilities are established for the stabilization of transition states and lowering of activation barriers due to the formation of cycles involving hydrogen bonds. The formation of eight-membered proton-transfer cycles and eight- or ten-membered stabilization cycles is preferable for the given reaction. The lower calculated magnitude of the barrier of the reaction proceeding by concert mechanism in methanol is 15.1 kcal mole−1. The reaction mechanism specificities associated with the formation of zwitterionic intermediates are discussed. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Theoretical Chemistry Accounts Springer Journals

Specificities of application of the supermolecule method to the calculation of reaction mechanisms in a protonodonor medium. Ethylene carbonate aminolysis in methanol

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Publisher
Springer Journals
Copyright
Copyright © 2017 by Springer-Verlag GmbH Germany
Subject
Chemistry; Theoretical and Computational Chemistry; Inorganic Chemistry; Organic Chemistry; Physical Chemistry; Atomic/Molecular Structure and Spectra
ISSN
1432-881X
eISSN
1432-2234
D.O.I.
10.1007/s00214-017-2124-9
Publisher site
See Article on Publisher Site

Abstract

The specificities of application of the supermolecule method to the calculation of mechanisms of reactions in a protonodonor medium are considered using as an example the reaction of methylamine with ethylene carbonate in methanol. The energies of non-interacting solvated reactants have been used as the reference levels for calculation of relative energies. The problems that result from using the energies of the pre-reaction complexes or the sums of the energies of infinitely separated reactants as the reference levels are noted. The optimal number of the solvent molecules necessary to comprehensively model the reaction under consideration is found. Two possibilities are established for the stabilization of transition states and lowering of activation barriers due to the formation of cycles involving hydrogen bonds. The formation of eight-membered proton-transfer cycles and eight- or ten-membered stabilization cycles is preferable for the given reaction. The lower calculated magnitude of the barrier of the reaction proceeding by concert mechanism in methanol is 15.1 kcal mole−1. The reaction mechanism specificities associated with the formation of zwitterionic intermediates are discussed.

Journal

Theoretical Chemistry AccountsSpringer Journals

Published: Aug 7, 2017

References

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