The electronic origin of unusually large nJFN coupling constants in some fluoroximes

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SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. I...

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Autores principales: Favaro, D.C., Contreras, R.H., Tormena, C.F.
Formato: JOUR
Materias:
nJFN through space coupling constants
dFN dependence
lone pairs interaction
overlap matrix
oxime
article
chemical structure
chemistry
electron
nuclear magnetic resonance spectroscopy
quantum theory
standard
Electrons
Magnetic Resonance Spectroscopy
Molecular Structure
Oximes
Quantum Theory
Reference Standards
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_07491581_v51_n6_p334_Favaro
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_07491581_v51_n6_p334_Favaro
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spelling todo:paper_07491581_v51_n6_p334_Favaro2023-10-03T15:39:33Z The electronic origin of unusually large nJFN coupling constants in some fluoroximes Favaro, D.C. Contreras, R.H. Tormena, C.F. nJFN through space coupling constants dFN dependence lone pairs interaction overlap matrix oxime article chemical structure chemistry electron nuclear magnetic resonance spectroscopy quantum theory standard Electrons Magnetic Resonance Spectroscopy Molecular Structure Oximes Quantum Theory Reference Standards SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as 'through overlapping orbital coupling'. Copyright © 2013 John Wiley & Sons, Ltd. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_07491581_v51_n6_p334_Favaro
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic nJFN through space coupling constants
dFN dependence
lone pairs interaction
overlap matrix
oxime
article
chemical structure
chemistry
electron
nuclear magnetic resonance spectroscopy
quantum theory
standard
Electrons
Magnetic Resonance Spectroscopy
Molecular Structure
Oximes
Quantum Theory
Reference Standards
spellingShingle nJFN through space coupling constants
dFN dependence
lone pairs interaction
overlap matrix
oxime
article
chemical structure
chemistry
electron
nuclear magnetic resonance spectroscopy
quantum theory
standard
Electrons
Magnetic Resonance Spectroscopy
Molecular Structure
Oximes
Quantum Theory
Reference Standards
Favaro, D.C.
Contreras, R.H.
Tormena, C.F.
The electronic origin of unusually large nJFN coupling constants in some fluoroximes
topic_facet nJFN through space coupling constants
dFN dependence
lone pairs interaction
overlap matrix
oxime
article
chemical structure
chemistry
electron
nuclear magnetic resonance spectroscopy
quantum theory
standard
Electrons
Magnetic Resonance Spectroscopy
Molecular Structure
Oximes
Quantum Theory
Reference Standards
description SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through-space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well-known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non-bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so-called through-space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through-space coupling, it should better be dubbed as 'through overlapping orbital coupling'. Copyright © 2013 John Wiley & Sons, Ltd.
format JOUR
author Favaro, D.C.
Contreras, R.H.
Tormena, C.F.
author_facet Favaro, D.C.
Contreras, R.H.
Tormena, C.F.
author_sort Favaro, D.C.
title The electronic origin of unusually large nJFN coupling constants in some fluoroximes
title_short The electronic origin of unusually large nJFN coupling constants in some fluoroximes
title_full The electronic origin of unusually large nJFN coupling constants in some fluoroximes
title_fullStr The electronic origin of unusually large nJFN coupling constants in some fluoroximes
title_full_unstemmed The electronic origin of unusually large nJFN coupling constants in some fluoroximes
title_sort electronic origin of unusually large njfn coupling constants in some fluoroximes
url http://hdl.handle.net/20.500.12110/paper_07491581_v51_n6_p334_Favaro
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