Vicinal NMR proton - Proton coupling constants. An NBO analysis

Angel L. Esteban; Maria P. Galache; Francisco Mora; Ernesto Díez; Jorge Casanueva; Jesús San Fabián; Verónica Barone; Juan E. Peralta; Ruben H. Contreras

doi:10.1021/jp0100811

Vicinal NMR proton - Proton coupling constants. An NBO analysis

Angel L. Esteban, Maria P. Galache, Francisco Mora, Ernesto Díez, Jorge Casanueva, Jesús San Fabián, Verónica Barone, Juan E. Peralta, Ruben H. Contreras

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Abstract

A method of natural bond orbital (NBO) interactions between bonds and antibonds, σ_m → σ_n*, has been developed for analyzing vicinal proton - proton coupling constants, ³J_HH. The contribution to ³J_HH from such an interaction σ_m → σ_n* is defined as J_mn* and is obtained following these three steps: (i) the SOS scheme is used to calculate ³J_HH; (ii) the same calculation is repeated after deleting the relevant off-diagonal elements in the NBO Fock matrix; (iii) J_mn* is obtained as the difference between those calculated in steps i and ii. Application of this method to the ethane and fluoroethane molecules shows that the main contribution to ³J_HH comes from the through space term while the substitution of a hydrogen in ethane by a fluorine changes this through space term and, in addition, gives a direct contribution to ³J_HH.

Original language	English
Pages (from-to)	5298-5303
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	105
Issue number	21
DOIs	https://doi.org/10.1021/jp0100811
State	Published - May 31 2001

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title = "Vicinal NMR proton - Proton coupling constants. An NBO analysis",

abstract = "A method of natural bond orbital (NBO) interactions between bonds and antibonds, σm → σn*, has been developed for analyzing vicinal proton - proton coupling constants, 3JHH. The contribution to 3JHH from such an interaction σm → σn* is defined as Jmn* and is obtained following these three steps: (i) the SOS scheme is used to calculate 3JHH; (ii) the same calculation is repeated after deleting the relevant off-diagonal elements in the NBO Fock matrix; (iii) Jmn* is obtained as the difference between those calculated in steps i and ii. Application of this method to the ethane and fluoroethane molecules shows that the main contribution to 3JHH comes from the through space term while the substitution of a hydrogen in ethane by a fluorine changes this through space term and, in addition, gives a direct contribution to 3JHH.",

author = "Esteban, {Angel L.} and Galache, {Maria P.} and Francisco Mora and Ernesto D{\'i}ez and Jorge Casanueva and {San Fabi{\'a}n}, Jes{\'u}s and Ver{\'o}nica Barone and Peralta, {Juan E.} and Contreras, {Ruben H.}",

year = "2001",

month = may,

day = "31",

doi = "10.1021/jp0100811",

language = "English",

volume = "105",

pages = "5298--5303",

journal = "Journal of Physical Chemistry A",

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publisher = "Journal of Physical Chemistry A",

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TY - JOUR

T1 - Vicinal NMR proton - Proton coupling constants. An NBO analysis

AU - Esteban, Angel L.

AU - Galache, Maria P.

AU - Mora, Francisco

AU - Díez, Ernesto

AU - Casanueva, Jorge

AU - San Fabián, Jesús

AU - Barone, Verónica

AU - Peralta, Juan E.

AU - Contreras, Ruben H.

PY - 2001/5/31

Y1 - 2001/5/31

N2 - A method of natural bond orbital (NBO) interactions between bonds and antibonds, σm → σn*, has been developed for analyzing vicinal proton - proton coupling constants, 3JHH. The contribution to 3JHH from such an interaction σm → σn* is defined as Jmn* and is obtained following these three steps: (i) the SOS scheme is used to calculate 3JHH; (ii) the same calculation is repeated after deleting the relevant off-diagonal elements in the NBO Fock matrix; (iii) Jmn* is obtained as the difference between those calculated in steps i and ii. Application of this method to the ethane and fluoroethane molecules shows that the main contribution to 3JHH comes from the through space term while the substitution of a hydrogen in ethane by a fluorine changes this through space term and, in addition, gives a direct contribution to 3JHH.

AB - A method of natural bond orbital (NBO) interactions between bonds and antibonds, σm → σn*, has been developed for analyzing vicinal proton - proton coupling constants, 3JHH. The contribution to 3JHH from such an interaction σm → σn* is defined as Jmn* and is obtained following these three steps: (i) the SOS scheme is used to calculate 3JHH; (ii) the same calculation is repeated after deleting the relevant off-diagonal elements in the NBO Fock matrix; (iii) Jmn* is obtained as the difference between those calculated in steps i and ii. Application of this method to the ethane and fluoroethane molecules shows that the main contribution to 3JHH comes from the through space term while the substitution of a hydrogen in ethane by a fluorine changes this through space term and, in addition, gives a direct contribution to 3JHH.

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U2 - 10.1021/jp0100811

DO - 10.1021/jp0100811

M3 - Article

AN - SCOPUS:0035979118

VL - 105

SP - 5298

EP - 5303

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 21

ER -

Vicinal NMR proton - Proton coupling constants. An NBO analysis

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