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dc.contributor.author
Laali, Kenneth K.
dc.contributor.author
Borosky, Gabriela Leonor
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dc.date.available
2015-10-01T18:52:20Z
dc.date.issued
2013-07
dc.identifier.citation
Laali, Kenneth K.; Borosky, Gabriela Leonor; α-Sulfur or α-fluorine - Which is more stabilizing for a carbocation? A computational study of electrophilic addition to HFCCH(SMe) and FC(R1)CR2(SMe) and related model systems; Elsevier Science SA; Journal of Fluorine Chemistry; 151; 7-2013; 26-31
dc.identifier.issn
0022-1139
dc.identifier.uri
http://hdl.handle.net/11336/2266
dc.description.abstract
Carbocations derived from protonation, methylation, and bromine addition to HFC55CH(SMe) (1) were studied by DFT [B3LYP/6-31G*, B3LYP/6-311G(3df,p), and B3LYP/aug-cc-pVTZ] and by MP2/6-31G* to examine relative carbocation stabilizing effects of a-SMe versus a-fluorine. The a-SMe carbocations 1aE+ and the unsymmetrical thiiranium ions 1cE+ were found to be considerably more stable than the corresponding a-fluorocarbenium ions 1bE+ . Study of protonation and methylation of FC(R1)55CR2(SMe) [R1 = H, R2 = SMe (2); R1 = F, R2 = H (3); R1 = F, R2 = SMe (4); R1 = Me, R2 = H (5); R1 = Me, R2 = SMe (6)] by B3LYP/6-31G* identified the corresponding unsymmetrical thiiranium cations as lowest energy minima, followed closely by the a-thiocarbenium ions. With 2, 4, and 6, skeletally rearranged a-thiocarbenium ions are formed by SMe migration. The a-SMe and the thiiranium cations are also favored relative to a- fluorocarbenium ions in protonation and methylation of the cyclic analogs 8 and 9. Computed NPA charges and the GIAO-derived 13C and 19F NMR chemical shifts underscore the significance of athiocarbocations and thiiranium ions in electrophilic addition to FC(R1)55CR2(SMe).
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier Science SA
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.subject
Α-F VERSUS Α-SME
dc.subject
CHARGE DELOCALIZATION
dc.subject
DFT
dc.subject
FLUOROCARBENIUM ION
dc.subject
THIIRANIUM ION
dc.subject
THIOCARBENIUM ION
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
α-Sulfur or α-fluorine - Which is more stabilizing for a carbocation? A computational study of electrophilic addition to HFCCH(SMe) and FC(R1)CR2(SMe) and related model systems
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-03-30 10:35:44.97925-03
dc.journal.volume
151
dc.journal.pagination
26-31
dc.journal.pais
Países Bajos
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dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Laali, Kenneth K.. University of Florida; Estados Unidos
dc.description.fil
Fil: Borosky, Gabriela Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Investigaciones en Físicoquímica de Córdoba; Argentina
dc.journal.title
Journal of Fluorine Chemistry
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022113913001504
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.jfluchem.2013.04.003
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