Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives
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 SS...
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paper:paper_10895639_v115_n22_p5684_Anizelli2023-06-08T16:06:29Z Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives Contreras, Rubén Horacio 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 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. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2011 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n22_p5684_Anizelli http://hdl.handle.net/20.500.12110/paper_10895639_v115_n22_p5684_Anizelli |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 Contreras, Rubén Horacio Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| topic_facet |
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 |
| description |
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. |
| author |
Contreras, Rubén Horacio |
| author_facet |
Contreras, Rubén Horacio |
| author_sort |
Contreras, Rubén Horacio |
| title |
Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| title_short |
Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| title_full |
Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| title_fullStr |
Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| title_full_unstemmed |
Effect of electronic interactions on NMR 1JCF and 2JCF couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| title_sort |
effect of electronic interactions on nmr 1jcf and 2jcf couplings in cis- and trans-4-t-butyl-2- fluorocyclohexanones and their alcohol derivatives |
| publishDate |
2011 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n22_p5684_Anizelli http://hdl.handle.net/20.500.12110/paper_10895639_v115_n22_p5684_Anizelli |
| work_keys_str_mv |
AT contrerasrubenhoracio effectofelectronicinteractionsonnmr1jcfand2jcfcouplingsincisandtrans4tbutyl2fluorocyclohexanonesandtheiralcoholderivatives |
| _version_ |
1768544515696623616 |