Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study

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A conceptual analysis of the CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) expressions that deconvolute NMR spin-spin coupling constants [Diz A. C.; Giribet C. G.; Ruiz de Azúa, M. C.; Contreras, R. H. Int. J. Quantum Chem. 1990, 37, 663.] into orbital co...

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Autores principales: Neto, Á.C., Dos Santos, F.P., Contreras, R.H., Rittner, R., Tormena, C.F.
Formato: JOUR
Materias:
Experiments
Nuclear magnetic resonance
Propane
Quantum chemistry
Sulfur compounds
AS models
Conceptual analysis
DFT studies
Electronic origins
Fermi contact terms
Hyperconjugative interactions
Localized orbitals
Orbital contributions
Propagator approaches
Spin couplings
Spin-spin coupling constants
Substituent effects
Spin dynamics
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_10895639_v112_n46_p11956_Neto
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_10895639_v112_n46_p11956_Neto2023-10-03T16:04:37Z Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study Neto, Á.C. Dos Santos, F.P. Contreras, R.H. Rittner, R. Tormena, C.F. Experiments Nuclear magnetic resonance Propane Quantum chemistry Sulfur compounds AS models Conceptual analysis DFT studies Electronic origins Fermi contact terms Hyperconjugative interactions Localized orbitals Orbital contributions Propagator approaches Spin couplings Spin-spin coupling constants Substituent effects Spin dynamics A conceptual analysis of the CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) expressions that deconvolute NMR spin-spin coupling constants [Diz A. C.; Giribet C. G.; Ruiz de Azúa, M. C.; Contreras, R. H. Int. J. Quantum Chem. 1990, 37, 663.] into orbital contributions can provide an in-depth insight into the features of the electronic molecular structure that originate a given 1JCH experimental trend. In this work, several 1-X-cyclopropane derivatives are taken as model compounds to apply such ideas to rationalize substituent effects on the Fermi contact term of 1JC1,H spin-spin coupling. It is shown that in this type of coupling, its experimental trend, as measured in this work, cannot be accounted for with only the "bond" and the "other bond" contributions, requiring the inclusion of "other antibonding contributions". Such effect is discussed in terms of hyperconjugative interactions. © 2008 American Chemical Society. 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_10895639_v112_n46_p11956_Neto
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Experiments
Nuclear magnetic resonance
Propane
Quantum chemistry
Sulfur compounds
AS models
Conceptual analysis
DFT studies
Electronic origins
Fermi contact terms
Hyperconjugative interactions
Localized orbitals
Orbital contributions
Propagator approaches
Spin couplings
Spin-spin coupling constants
Substituent effects
Spin dynamics
spellingShingle Experiments
Nuclear magnetic resonance
Propane
Quantum chemistry
Sulfur compounds
AS models
Conceptual analysis
DFT studies
Electronic origins
Fermi contact terms
Hyperconjugative interactions
Localized orbitals
Orbital contributions
Propagator approaches
Spin couplings
Spin-spin coupling constants
Substituent effects
Spin dynamics
Neto, Á.C.
Dos Santos, F.P.
Contreras, R.H.
Rittner, R.
Tormena, C.F.
Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
topic_facet Experiments
Nuclear magnetic resonance
Propane
Quantum chemistry
Sulfur compounds
AS models
Conceptual analysis
DFT studies
Electronic origins
Fermi contact terms
Hyperconjugative interactions
Localized orbitals
Orbital contributions
Propagator approaches
Spin couplings
Spin-spin coupling constants
Substituent effects
Spin dynamics
description A conceptual analysis of the CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) expressions that deconvolute NMR spin-spin coupling constants [Diz A. C.; Giribet C. G.; Ruiz de Azúa, M. C.; Contreras, R. H. Int. J. Quantum Chem. 1990, 37, 663.] into orbital contributions can provide an in-depth insight into the features of the electronic molecular structure that originate a given 1JCH experimental trend. In this work, several 1-X-cyclopropane derivatives are taken as model compounds to apply such ideas to rationalize substituent effects on the Fermi contact term of 1JC1,H spin-spin coupling. It is shown that in this type of coupling, its experimental trend, as measured in this work, cannot be accounted for with only the "bond" and the "other bond" contributions, requiring the inclusion of "other antibonding contributions". Such effect is discussed in terms of hyperconjugative interactions. © 2008 American Chemical Society.
format JOUR
author Neto, Á.C.
Dos Santos, F.P.
Contreras, R.H.
Rittner, R.
Tormena, C.F.
author_facet Neto, Á.C.
Dos Santos, F.P.
Contreras, R.H.
Rittner, R.
Tormena, C.F.
author_sort Neto, Á.C.
title Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
title_short Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
title_full Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
title_fullStr Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
title_full_unstemmed Analysis of the electronic origin of the1JCH spin-spin coupling trend in 1-X-cyclopropanes: Experimental and DFT study
title_sort analysis of the electronic origin of the1jch spin-spin coupling trend in 1-x-cyclopropanes: experimental and dft study
url http://hdl.handle.net/20.500.12110/paper_10895639_v112_n46_p11956_Neto
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