DUGiDocsAn analysis of the isomerization energies of 1,2-/1,3-diazacyclobutadiene, pyrazole/imidazole, and pyridazine/pyrimidine with the turn-upside-down approach
dc.contributor.author
dc.date.accessioned
2015-10-28T07:06:16Z
dc.date.available
2015-10-28T07:06:16Z
dc.date.issued
2011-11-04
dc.identifier.issn
0022-3263
dc.identifier.uri
dc.description.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 σ-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
dc.description.sponsorship
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
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2008-03077/ES/CLUSTERES METALICOS Y SEMIMETALICOS. ESTUDIOS DE AROMATICIDAD Y REACTIVIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2008-06532/ES/REACTIVIDAD Y ENLACE QUIMICO EN BIOMEDICINA Y QUIMICA (BIO)INORGANICA/
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
AGAUR/2009-2014/2009 SGR-637
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/jo201639k
dc.relation.ispartof
© Journal of Organic Chemistry, 2011, vol. 76, núm. 21, p. 8913-8921
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
An analysis of the isomerization energies of 1,2-/1,3-diazacyclobutadiene, pyrazole/imidazole, and pyridazine/pyrimidine with the turn-upside-down approach
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
015420
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-6904