Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/8234
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dc.contributor.authorArnaut, Luís G.-
dc.contributor.authorFormosinho, Sebastião J.-
dc.date.accessioned2009-02-09T14:31:18Z-
dc.date.available2009-02-09T14:31:18Z-
dc.date.issued2007en_US
dc.identifier.citationChemistry - A European Journal. 13:28 (2007) 8018-8028en_US
dc.identifier.urihttp://hdl.handle.net/10316/8234-
dc.description.abstractThe energy barriers of symmetrical methyl exchanges in the gas phase have been calculated with the reaction path of the intersecting/interacting-state model (ISM). Reactive bond lengths increase down a column of the Periodic Table and compensate for the decrease in the force constants, which explains the near constancy of the intrinsic barriers in the following series of nucleophiles: F-≈Cl-≈Br-≈I-. This compensation is absent along the rows of the Periodic Table and the trend in the reactivity is dominated by the increase in the electrophilicity index of the nucleophile in the series C<N<O<F. Solvent effects have been quantitatively incorporated into the ISM model through a correlation between electrophilicity and the solvent acceptor number. This correlation is transferable between nucleophiles and solvents and allows the methyl transfer rate constants in solution to be calculated with remarkable simplicity and accuracy. The relationship between the SN2 and electron-transfer mechanisms is clarified and it is shown that smaller solvent static effects should be expected for electron transfer in the absence of a thermodynamic driving force.en_US
dc.language.isoengeng
dc.rightsopenAccesseng
dc.titleThe Rates of SN2 Reactions and Their Relation to Molecular and Solvent Propertiesen_US
dc.typearticleen_US
dc.identifier.doi10.1002/chem.200700276en_US
uc.controloAutoridadeSim-
item.fulltextCom Texto completo-
item.grantfulltextopen-
item.languageiso639-1en-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0002-3223-4819-
crisitem.author.orcid0000-0001-6607-0026-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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