Issue 14, 2014

Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels–Alder reactions

Abstract

We have computationally compared three Diels–Alder cycloadditions involving cyclopentadiene and substituted ethylenes; one of the reactions is synchronous, while the others are slightly or highly asynchronous. Synchronicity and weak asynchronicity are characterized by the reaction force constant κ(ξ) having just a single minimum in the transition region along the intrinsic reaction coordinate ξ, while for high asynchronicity κ(ξ) has a negative maximum with minima on both sides. The electron localization function (ELF) shows that the features of κ(ξ) can be directly related to the formation of the new C–C bonds between the diene and the dienophile. There is thus a striking complementarity between κ(ξ) and ELF; κ(ξ) identifies the key points along ξ and ELF describes what is happening at those points.

Graphical abstract: Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels–Alder reactions

Article information

Article type
Paper
Submitted
11 Nov 2013
Accepted
06 Feb 2014
First published
06 Feb 2014

Phys. Chem. Chem. Phys., 2014,16, 6726-6734

Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels–Alder reactions

D. Yepes, J. S. Murray, P. Pérez, L. R. Domingo, P. Politzer and P. Jaque, Phys. Chem. Chem. Phys., 2014, 16, 6726 DOI: 10.1039/C3CP54766C

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