Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives

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Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this...

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Autor principal: Contreras, Rubén Horacio
Publicado: 2011
Materias:
Cholesterol levels
Coupling constants
Ezetimibe
Fermi contact
Fluorobenzene
Hybrid functionals
Hyperconjugative interactions
NMR coupling
Paramagnetic spins
Qualitative approach
Second orders
Similar degree
Spin-spin coupling constants
Substituent effect
Virtual excitations
Virtual orbitals
Paramagnetism
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n7_p1272_Vilcachagua
http://hdl.handle.net/20.500.12110/paper_10895639_v115_n7_p1272_Vilcachagua
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_10895639_v115_n7_p1272_Vilcachagua
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spelling paper:paper_10895639_v115_n7_p1272_Vilcachagua2023-06-08T16:06:30Z Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives Contreras, Rubén Horacio Cholesterol levels Coupling constants Ezetimibe Fermi contact Fluorobenzene Hybrid functionals Hyperconjugative interactions NMR coupling Paramagnetic spins Qualitative approach Second orders Similar degree Spin-spin coupling constants Substituent effect Virtual excitations Virtual orbitals Paramagnetism Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 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_n7_p1272_Vilcachagua http://hdl.handle.net/20.500.12110/paper_10895639_v115_n7_p1272_Vilcachagua
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Cholesterol levels
Coupling constants
Ezetimibe
Fermi contact
Fluorobenzene
Hybrid functionals
Hyperconjugative interactions
NMR coupling
Paramagnetic spins
Qualitative approach
Second orders
Similar degree
Spin-spin coupling constants
Substituent effect
Virtual excitations
Virtual orbitals
Paramagnetism
spellingShingle Cholesterol levels
Coupling constants
Ezetimibe
Fermi contact
Fluorobenzene
Hybrid functionals
Hyperconjugative interactions
NMR coupling
Paramagnetic spins
Qualitative approach
Second orders
Similar degree
Spin-spin coupling constants
Substituent effect
Virtual excitations
Virtual orbitals
Paramagnetism
Contreras, Rubén Horacio
Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
topic_facet Cholesterol levels
Coupling constants
Ezetimibe
Fermi contact
Fluorobenzene
Hybrid functionals
Hyperconjugative interactions
NMR coupling
Paramagnetic spins
Qualitative approach
Second orders
Similar degree
Spin-spin coupling constants
Substituent effect
Virtual excitations
Virtual orbitals
Paramagnetism
description Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of 1JCF NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH2; NO 2) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for 1JCF spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the 1JCF with those observed for the SOPPA(CCSD) method was obtained. The 1JCF SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to 1JCF SSCCs is discussed. © 2011 American Chemical Society.
author Contreras, Rubén Horacio
author_facet Contreras, Rubén Horacio
author_sort Contreras, Rubén Horacio
title Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_short Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_full Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_fullStr Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_full_unstemmed Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1 JCF coupling constants in fluorobenzene derivatives
title_sort experimental, soppa(ccsd), and dft analysis of substitutent effects on nmr 1 jcf coupling constants in fluorobenzene derivatives
publishDate 2011
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v115_n7_p1272_Vilcachagua
http://hdl.handle.net/20.500.12110/paper_10895639_v115_n7_p1272_Vilcachagua
work_keys_str_mv AT contrerasrubenhoracio experimentalsoppaccsdanddftanalysisofsubstitutenteffectsonnmr1jcfcouplingconstantsinfluorobenzenederivatives
_version_ 1768543288366727168

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