Theoretical perspectives on carbocation chemistry from energy decomposition analysis

Theoretical perspectives on carbocation chemistry from energy decomposition analysis Understanding carbocation formation is a central concern for all chemical sciences. The widely accepted explanation in terms of inductive/field and delocalization effects is based on quantities that are not straightforwardly computed in popular electronic structure methods. This work reports an alternative approach to the carbocation formation problem based on energy decomposition analysis, more specifically, CMOEDA. The order of stability for carbocations formation was successfully accounted in terms of the energy components. The focus of the analysis shifts from the product of the reaction, i.e., the carbocation itself, to the reactant neutral molecule. Notably, exchange repulsions are the largest energy contribution to increase carbocation stability in the order methyl, primary, secondary and tertiary. Polarization (orbital relaxation) plays a secondary role. Insertion of bulky groups increases the repulsion with the incipient anion (a hydride ion) and decreases the strength of the C–H bond. This pattern is confirmed for several other hydrocarbon cases. Additional systems like halomethanes, amino- and nitro-derivatives are also described. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Theoretical Chemistry Accounts Springer Journals

Theoretical perspectives on carbocation chemistry from energy decomposition analysis

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Publisher
Springer Journals
Copyright
Copyright © 2018 by Springer-Verlag GmbH Germany, part of Springer Nature
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/s00214-018-2232-1
Publisher site
See Article on Publisher Site

Abstract

Understanding carbocation formation is a central concern for all chemical sciences. The widely accepted explanation in terms of inductive/field and delocalization effects is based on quantities that are not straightforwardly computed in popular electronic structure methods. This work reports an alternative approach to the carbocation formation problem based on energy decomposition analysis, more specifically, CMOEDA. The order of stability for carbocations formation was successfully accounted in terms of the energy components. The focus of the analysis shifts from the product of the reaction, i.e., the carbocation itself, to the reactant neutral molecule. Notably, exchange repulsions are the largest energy contribution to increase carbocation stability in the order methyl, primary, secondary and tertiary. Polarization (orbital relaxation) plays a secondary role. Insertion of bulky groups increases the repulsion with the incipient anion (a hydride ion) and decreases the strength of the C–H bond. This pattern is confirmed for several other hydrocarbon cases. Additional systems like halomethanes, amino- and nitro-derivatives are also described.

Journal

Theoretical Chemistry AccountsSpringer Journals

Published: Mar 13, 2018

References

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