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Abstract:

In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on 1JCF and 2J CF NMR spin-spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of 2JCF SSCC in cis- 4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds. © 2011 American Chemical Society.

Registro:

Documento: Artículo
Título:Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives
Autor:Anizelli, P.R.; Favaro, D.C.; Contreras, R.H.; Tormena, C.F.
Filiación:Chemistry Institute, University of Campinas, Post Office Box 6154, 13084-971 Campinas, SP, Brazil
Department of Physics, FCEyN, University of Buenos Aires and IFIBA-CONICET, Buenos Aires, Argentina
Palabras clave:Alcohol derivatives; Electronic interactions; Fermi contact; Hydrogen-bond interactions; Qualitative analysis; Spin orbits; Spin-spin coupling constants; Steric compression; Transmission mechanisms; Hydrogen; Hydrogen bonds; Paramagnetism; Electron spin resonance spectroscopy; 4 tert butyl 2 fluorocyclohexanone; 4-tert-butyl-2-fluorocyclohexanone; alcohol derivative; cyclohexanone derivative; article; chemical structure; chemistry; electron; nuclear magnetic resonance spectroscopy; quantum theory; standard; stereoisomerism; synthesis; Alcohols; Cyclohexanones; Electrons; Magnetic Resonance Spectroscopy; Molecular Structure; Quantum Theory; Reference Standards; Stereoisomerism
Año:2011
Volumen:115
Número:22
Página de inicio:5684
Página de fin:5692
DOI: http://dx.doi.org/10.1021/jp202592c
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
CAS:4-tert-butyl-2-fluorocyclohexanone; Alcohols; Cyclohexanones
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n22_p5684_Anizelli

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Citas:

---------- APA ----------
Anizelli, P.R., Favaro, D.C., Contreras, R.H. & Tormena, C.F. (2011) . Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives. Journal of Physical Chemistry A, 115(22), 5684-5692.
http://dx.doi.org/10.1021/jp202592c
---------- CHICAGO ----------
Anizelli, P.R., Favaro, D.C., Contreras, R.H., Tormena, C.F. "Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives" . Journal of Physical Chemistry A 115, no. 22 (2011) : 5684-5692.
http://dx.doi.org/10.1021/jp202592c
---------- MLA ----------
Anizelli, P.R., Favaro, D.C., Contreras, R.H., Tormena, C.F. "Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives" . Journal of Physical Chemistry A, vol. 115, no. 22, 2011, pp. 5684-5692.
http://dx.doi.org/10.1021/jp202592c
---------- VANCOUVER ----------
Anizelli, P.R., Favaro, D.C., Contreras, R.H., Tormena, C.F. Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives. J Phys Chem A. 2011;115(22):5684-5692.
http://dx.doi.org/10.1021/jp202592c