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An analysis of the isomerization energies of 1,2-/1,3-diazacyclobutadiene, pyrazole/imidazole, and pyridazine/pyrimidine with the turn-upside-down approach

The isomerization energies of 1,2- and 1,3-diazacyclobutadiene, pyrazole and imidazole, and pyridazine and pyrimidine are 10.6, 9.4, and 20.9 kcal/mol, respectively, at the BP86/TZ2P level of theory. These energies are analyzed using a Morokuma-like energy decomposition analysis in conjunction with what we have called turn-upside-down approach. Our results indicate that, in the three cases, the higher stability of the 1,3-isomers is not due to lower Pauli repulsions but because of the more favorable 蟽-orbital interactions involved in the formation of two C-N bonds in comparison with the generation of C-C and N-N bonds in the 1,2-isomers

We thank the following organizations for financial support: the Ministerio de Ciencia e Innovacion (MICINN, Project Nos. CTQ2008-03077/BQU, CTQ2008-06532/BQU, and CTQ2011-23156/BQU, Ramon y Cajal contract to J.P., and FPI fellowship to M.E.H.) and the DIUE of the Generalitat de Catalunya (project no. 2009SGR637). W.T. thanks FONDECYT (Grant No. 1109043). We acknowledge helpful comments from Prof. Dr. F. Matthias Bickelhaupt. Excellent service by the Centre de Supercomputacio de Catalunya (CESCA) is gratefully acknowledged

漏 Journal of Organic Chemistry, 2011, vol. 76, n煤m. 21, p. 8913-8921

American Chemical Society (ACS)

Manager: Ministerio de Educaci贸n y Ciencia (Espanya)
Ministerio de Ciencia e Innovaci贸n (Espanya)
Generalitat de Catalunya. Ag猫ncia de Gesti贸 d鈥橝juts Universitaris i de Recerca
Author: El Hamdi Lahfid, Majid
Tiznado, William
Poater i Teixidor, Jordi
Sol脿 i Puig, Miquel
Date: 2011 November 4
Abstract: The isomerization energies of 1,2- and 1,3-diazacyclobutadiene, pyrazole and imidazole, and pyridazine and pyrimidine are 10.6, 9.4, and 20.9 kcal/mol, respectively, at the BP86/TZ2P level of theory. These energies are analyzed using a Morokuma-like energy decomposition analysis in conjunction with what we have called turn-upside-down approach. Our results indicate that, in the three cases, the higher stability of the 1,3-isomers is not due to lower Pauli repulsions but because of the more favorable 蟽-orbital interactions involved in the formation of two C-N bonds in comparison with the generation of C-C and N-N bonds in the 1,2-isomers
We thank the following organizations for financial support: the Ministerio de Ciencia e Innovacion (MICINN, Project Nos. CTQ2008-03077/BQU, CTQ2008-06532/BQU, and CTQ2011-23156/BQU, Ramon y Cajal contract to J.P., and FPI fellowship to M.E.H.) and the DIUE of the Generalitat de Catalunya (project no. 2009SGR637). W.T. thanks FONDECYT (Grant No. 1109043). We acknowledge helpful comments from Prof. Dr. F. Matthias Bickelhaupt. Excellent service by the Centre de Supercomputacio de Catalunya (CESCA) is gratefully acknowledged
Format: application/pdf
Citation: 015420
ISSN: 0022-3263 (versi贸 paper)
1520-6904 (versi贸 electr貌nica)
Document access: http://hdl.handle.net/10256/11390
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MEC/PN 2009-2011/CTQ2008-03077/BQU
MEC/PN 2009-2011/CTQ2008-06532/BQU
MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
Reproducci贸 digital del document publicat a: http://dx.doi.org/10.1021/jo201639k
Articles publicats (D-Q)
Is part of: 漏 Journal of Organic Chemistry, 2011, vol. 76, n煤m. 21, p. 8913-8921
Rights: Tots els drets reservats
Subject: Isomeritzaci贸
Isomerization
Title: An analysis of the isomerization energies of 1,2-/1,3-diazacyclobutadiene, pyrazole/imidazole, and pyridazine/pyrimidine with the turn-upside-down approach
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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