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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.

Registro:

Documento: Artículo
Título:Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study
Autor:Neto, A.C.; Ducati, L.C.; Rittner, R.; Tormena, C.F.; Contreras, R.H.; Frenking, G.
Filiación:Chemistry Institute, State University of Campinas, Caixa Postal 6154, 13084-971 Campinas, SP, Brazil
Department of Physics, FCEyN, University of Buenos Aires and CONICET, Buenos Aires, Argentina
Philipps-Universität Marburg, Hans-Meerwein-Strasse, Marburg, Germany
Año:2009
Volumen:5
Número:9
Página de inicio:2222
Página de fin:2228
DOI: http://dx.doi.org/10.1021/ct800520w
Título revista:Journal of Chemical Theory and Computation
Título revista abreviado:J. Chem. Theory Comput.
ISSN:15499618
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15499618_v5_n9_p2222_Neto

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Citas:

---------- APA ----------
Neto, A.C., Ducati, L.C., Rittner, R., Tormena, C.F., Contreras, R.H. & Frenking, G. (2009) . Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study. Journal of Chemical Theory and Computation, 5(9), 2222-2228.
http://dx.doi.org/10.1021/ct800520w
---------- CHICAGO ----------
Neto, A.C., Ducati, L.C., Rittner, R., Tormena, C.F., Contreras, R.H., Frenking, G. "Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study" . Journal of Chemical Theory and Computation 5, no. 9 (2009) : 2222-2228.
http://dx.doi.org/10.1021/ct800520w
---------- MLA ----------
Neto, A.C., Ducati, L.C., Rittner, R., Tormena, C.F., Contreras, R.H., Frenking, G. "Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study" . Journal of Chemical Theory and Computation, vol. 5, no. 9, 2009, pp. 2222-2228.
http://dx.doi.org/10.1021/ct800520w
---------- VANCOUVER ----------
Neto, A.C., Ducati, L.C., Rittner, R., Tormena, C.F., Contreras, R.H., Frenking, G. Heavy halogen atom effect on 13C NMR chemical shifts in monohalo derivatives of cyclohexane and pyran. Experimental and theoretical study. J. Chem. Theory Comput. 2009;5(9):2222-2228.
http://dx.doi.org/10.1021/ct800520w