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dc.contributor.author
Neto, Alvaro Cunha
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Ducati, Lucas C.
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Rittner, Roberto
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Tormena, Cláudio F.
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Contreras, Ruben Horacio
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Frenking, Gernot
dc.date.available
2018-10-01T16:43:48Z
dc.date.issued
2009-07
dc.identifier.citation
Neto, Alvaro Cunha; Ducati, Lucas C.; Rittner, Roberto; Tormena, Cláudio F.; Contreras, Ruben Horacio; et al.; Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study; American Chemical Society; Journal of Chemical Theory and Computation; 5; 9; 7-2009; 2222-2228
dc.identifier.issn
1549-9618
dc.identifier.uri
http://hdl.handle.net/11336/61365
dc.description.abstract
As a first step, a qualitative analysis of the spin-orbit operator was performed to predict the kind of organic compounds, where it could be expected that the SO/FC (spin-orbit/Fermi contact) and SO/SD (spin-orbit/spin dipolar) yield unusually small contributions to the "heavy atom effect" on 13C SCSs (substituent chemical shifts). This analysis led to the conclusion that compounds presenting strong hyperconjugative interactions involving the σ*C-X orbital (X = halogen) are good examples where such effects can be expected to take place. On the basis of such results, the following set of model compounds was chosen: 2-eq-halocyclohexane (2-eq), 2-ax-halocyclohexane (2-ax), and 2-ax-halopyran (3), to measure 13C SCSs. Such experimental values, as well as those of methane and halomethanes taken from the literature, were compared to calculated values at a nonrelativistic approach using B3LYP, and at a relativistic approach with BP86 using scalar ZORA, spin-orbit ZORA, scalar PAULI, and spin-orbit PAULI. Results from relativistic calculations are in agreement with the trends predicted by the qualitative model discussed in this work. © 2009 American Chemical Society.
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Heavy Atom Effect
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Spin-Orbit
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Hyperconjugative Interactions
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13-C Chemical Shift
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Astronomía
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Ciencias Físicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-10-01T14:24:30Z
dc.journal.volume
5
dc.journal.number
9
dc.journal.pagination
2222-2228
dc.journal.pais
Estados Unidos
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Washington DC
dc.description.fil
Fil: Neto, Alvaro Cunha. Universidade Estadual de Campinas; Brasil
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Fil: Ducati, Lucas C.. Universidade Estadual de Campinas; Brasil
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Fil: Rittner, Roberto. Universidade Estadual de Campinas; Brasil
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Fil: Tormena, Cláudio F.. Universidade Estadual de Campinas; Brasil
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Fil: Contreras, Ruben Horacio. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina
dc.description.fil
Fil: Frenking, Gernot. Philipps-universität Marburg; Alemania
dc.journal.title
Journal of Chemical Theory and Computation
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ct800520w
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