Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study

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One- two- and three 13C, 13C (n = 1, 2, 3) scalar couplings, nJ(C,C) in a set of pyrimidine derivatives were studied both experimentally at natural abundance and theoretically by their DFT calculation of all four contributions. Trends of non-contact terms are discussed and substituent effects are ra...

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Autores principales:	Peralta, Juan Ernesto, Contreras, Rubén Horacio
Publicado:	2004
Materias:	13C NMR Dual path transmission Hyperconjugative interactions J(C,C) scalar couplings Lone-pair orientation effect NMR Pyrimidines benzene carbon 13 nitrogen derivative pyridine pyrimidine derivative article carbon nuclear magnetic resonance chemical interaction density functional theory molecular model substitution reaction
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v42_n11_p938_DeKowalewski http://hdl.handle.net/20.500.12110/paper_07491581_v42_n11_p938_DeKowalewski
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_07491581_v42_n11_p938_DeKowalewski
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spelling	paper:paper_07491581_v42_n11_p938_DeKowalewski2023-06-08T15:45:35Z Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study Peralta, Juan Ernesto Contreras, Rubén Horacio 13C NMR Dual path transmission Hyperconjugative interactions J(C,C) scalar couplings Lone-pair orientation effect NMR Pyrimidines benzene carbon 13 nitrogen derivative pyridine pyrimidine derivative article carbon nuclear magnetic resonance chemical interaction density functional theory molecular model substitution reaction One- two- and three 13C, 13C (n = 1, 2, 3) scalar couplings, nJ(C,C) in a set of pyrimidine derivatives were studied both experimentally at natural abundance and theoretically by their DFT calculation of all four contributions. Trends of non-contact terms are discussed and substituent effects are rationalized, comparing some of them with the corresponding values in benzene and pyridine. Although substituent effects on non-contact terms are relatively important, the whole trend is dominated by the Fermi contact term. According to the current literature, substituent effects on 1J(C,C) couplings in benzene derivatives are dominated by the inductive effect, which, apparently, is also the case in nitrogen heteroaromatic compounds. However, some differences observed in this work for substituent effects on 1J(C,C) couplings in pyrimidine derivatives suggest that in the latter type of compounds substituent effects can be affected by the orientation of the ring nitrogen lone pairs. Copyright © 2004 John Wiley & Sons, Ltd. Fil:Peralta, J.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Contreras, R.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2004 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v42_n11_p938_DeKowalewski http://hdl.handle.net/20.500.12110/paper_07491581_v42_n11_p938_DeKowalewski
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	13C NMR Dual path transmission Hyperconjugative interactions J(C,C) scalar couplings Lone-pair orientation effect NMR Pyrimidines benzene carbon 13 nitrogen derivative pyridine pyrimidine derivative article carbon nuclear magnetic resonance chemical interaction density functional theory molecular model substitution reaction
spellingShingle	13C NMR Dual path transmission Hyperconjugative interactions J(C,C) scalar couplings Lone-pair orientation effect NMR Pyrimidines benzene carbon 13 nitrogen derivative pyridine pyrimidine derivative article carbon nuclear magnetic resonance chemical interaction density functional theory molecular model substitution reaction Peralta, Juan Ernesto Contreras, Rubén Horacio Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
topic_facet	13C NMR Dual path transmission Hyperconjugative interactions J(C,C) scalar couplings Lone-pair orientation effect NMR Pyrimidines benzene carbon 13 nitrogen derivative pyridine pyrimidine derivative article carbon nuclear magnetic resonance chemical interaction density functional theory molecular model substitution reaction
description	One- two- and three 13C, 13C (n = 1, 2, 3) scalar couplings, nJ(C,C) in a set of pyrimidine derivatives were studied both experimentally at natural abundance and theoretically by their DFT calculation of all four contributions. Trends of non-contact terms are discussed and substituent effects are rationalized, comparing some of them with the corresponding values in benzene and pyridine. Although substituent effects on non-contact terms are relatively important, the whole trend is dominated by the Fermi contact term. According to the current literature, substituent effects on 1J(C,C) couplings in benzene derivatives are dominated by the inductive effect, which, apparently, is also the case in nitrogen heteroaromatic compounds. However, some differences observed in this work for substituent effects on 1J(C,C) couplings in pyrimidine derivatives suggest that in the latter type of compounds substituent effects can be affected by the orientation of the ring nitrogen lone pairs. Copyright © 2004 John Wiley & Sons, Ltd.
author	Peralta, Juan Ernesto Contreras, Rubén Horacio
author_facet	Peralta, Juan Ernesto Contreras, Rubén Horacio
author_sort	Peralta, Juan Ernesto
title	Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
title_short	Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
title_full	Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
title_fullStr	Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
title_full_unstemmed	Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study
title_sort	substituent effects on scalar j(13c, 13c) couplings in pyrimidines. an experimental and dft study
publishDate	2004
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07491581_v42_n11_p938_DeKowalewski http://hdl.handle.net/20.500.12110/paper_07491581_v42_n11_p938_DeKowalewski
work_keys_str_mv	AT peraltajuanernesto substituenteffectsonscalarj13c13ccouplingsinpyrimidinesanexperimentalanddftstudy AT contrerasrubenhoracio substituenteffectsonscalarj13c13ccouplingsinpyrimidinesanexperimentalanddftstudy
_version_	1768543997039476736

Substituent effects on scalar J(13C, 13C) couplings in pyrimidines. An experimental and DFT study

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