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| Campo DC | Valor | Lengua/Idioma |
|---|---|---|
| dc.provenance | CONICET | - |
| dc.creator | Laali, Kenneth K. | - |
| dc.creator | Borosky, Gabriela Leonor | - |
| dc.date | 2015-10-01T18:52:20Z | - |
| dc.date | 2015-10-01T18:52:20Z | - |
| dc.date | 2013-07 | - |
| dc.date | 2016-03-30 10:35:44.97925-03 | - |
| dc.date.accessioned | 2019-04-29T15:32:59Z | - |
| dc.date.available | 2019-04-29T15:32:59Z | - |
| dc.date.issued | 2013-07 | - |
| dc.identifier | 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 HFC=CH(SMe) and FC(R1)=CR2(SMe) and related model systems; Elsevier; Journal of Fluorine Chemistry; 151; 7-2013; 26-31 | - |
| dc.identifier | 0022-1139 | - |
| dc.identifier | http://hdl.handle.net/11336/2266 | - |
| dc.identifier.uri | http://rodna.bn.gov.ar:8080/jspui/handle/bnmm/296298 | - |
| dc.description | 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.description | Fil: Laali, Kenneth K.. University of North Florida. Department of Chemistry; Estados Unidos de América; | - |
| dc.description | Fil: Borosky, Gabriela Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Investigaciones en Físicoquímica de Córdoba; Argentina; | - |
| dc.format | application/pdf | - |
| dc.format | application/pdf | - |
| dc.language | eng | - |
| dc.publisher | Elsevier | - |
| dc.relation | info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022113913001504 | - |
| dc.relation | info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.jfluchem.2013.04.003 | - |
| dc.rights | info:eu-repo/semantics/restrictedAccess | - |
| dc.rights | https://creativecommons.org/licenses/by-nc-nd/2.5/ar/ | - |
| dc.source | reponame:CONICET Digital (CONICET) | - |
| dc.source | instname:Consejo Nacional de Investigaciones Científicas y Técnicas | - |
| dc.source | instacron:CONICET | - |
| dc.source.uri | http://hdl.handle.net/11336/2266 | - |
| dc.subject | ALPHA-F VERSUS ALPHA-SME | - |
| dc.subject | FLUOROCARBENIUM ION | - |
| dc.subject | THIOCARBENIUM ION | - |
| dc.subject | THIIRANIUIM ION | - |
| dc.subject | Charge delocalization | - |
| dc.subject | DFT | - |
| dc.subject | Físico-Química, Ciencia de los Polímeros, Electroquímica | - |
| dc.subject | Ciencias Químicas | - |
| dc.subject | CIENCIAS NATURALES Y EXACTAS | - |
| dc.title | α-sulfur or α-fluorine ̶ Which is more stabilizing for a carbocation? A computational study of electrophilic addition to HFC=CH(SMe) and FC(R1)=CR2(SMe) and related model systems | - |
| dc.type | info:eu-repo/semantics/article | - |
| dc.type | info:eu-repo/semantics/publishedVersion | - |
| dc.type | info:ar-repo/semantics/articulo | - |
| Aparece en las colecciones: | CONICET | |
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