Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene

An IPPP-INDO analysis of PC couplings is carried out in 7-(phosphamethyl) norbornene for the anti and syn conformations. A strong orientational effect of the P lone pair is expected to be responsible for the differences in the coupling values between conformations. Total couplings are decomposed int...

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Autores principales: Aucar, Gustavo A., Giribet, Claudia Gloria, Diz, Agustín Carlos, Contreras, Rubén Horacio
Publicado: 1988
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v164_n1-2_p1_Aucar
http://hdl.handle.net/20.500.12110/paper_01661280_v164_n1-2_p1_Aucar
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_01661280_v164_n1-2_p1_Aucar
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spelling paper:paper_01661280_v164_n1-2_p1_Aucar2023-06-08T15:15:08Z Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene Aucar, Gustavo A. Giribet, Claudia Gloria Diz, Agustín Carlos Contreras, Rubén Horacio An IPPP-INDO analysis of PC couplings is carried out in 7-(phosphamethyl) norbornene for the anti and syn conformations. A strong orientational effect of the P lone pair is expected to be responsible for the differences in the coupling values between conformations. Total couplings are decomposed into through-space and through-bond components. Further analysis of the through-space Fermi contact term is carried out by resolving it into contributions given by different "through-space coupling pathways", each pathway being defined by excitations which are amenable to direct analysis using the inner-projected polarization propagator technique. The experimental trends of PC couplings in both conformations are closely reproduced. The differences between both conformations are found to be ruled by: (i) the orientation of the P lone pair, which is shown to be an efficient means of transmitting the spin information; (ii) the transmission through the CH rear lobe; and (iii) the orientational effect of the PC antibonding molecular orbital. From (iii) the important role played by vacant molecular orbitals is also brought to attention. © 1988. Fil:Aucar, G.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Giribet, C.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Diz, A.C. 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. 1988 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v164_n1-2_p1_Aucar http://hdl.handle.net/20.500.12110/paper_01661280_v164_n1-2_p1_Aucar
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description An IPPP-INDO analysis of PC couplings is carried out in 7-(phosphamethyl) norbornene for the anti and syn conformations. A strong orientational effect of the P lone pair is expected to be responsible for the differences in the coupling values between conformations. Total couplings are decomposed into through-space and through-bond components. Further analysis of the through-space Fermi contact term is carried out by resolving it into contributions given by different "through-space coupling pathways", each pathway being defined by excitations which are amenable to direct analysis using the inner-projected polarization propagator technique. The experimental trends of PC couplings in both conformations are closely reproduced. The differences between both conformations are found to be ruled by: (i) the orientation of the P lone pair, which is shown to be an efficient means of transmitting the spin information; (ii) the transmission through the CH rear lobe; and (iii) the orientational effect of the PC antibonding molecular orbital. From (iii) the important role played by vacant molecular orbitals is also brought to attention. © 1988.
author Aucar, Gustavo A.
Giribet, Claudia Gloria
Diz, Agustín Carlos
Contreras, Rubén Horacio
spellingShingle Aucar, Gustavo A.
Giribet, Claudia Gloria
Diz, Agustín Carlos
Contreras, Rubén Horacio
Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
author_facet Aucar, Gustavo A.
Giribet, Claudia Gloria
Diz, Agustín Carlos
Contreras, Rubén Horacio
author_sort Aucar, Gustavo A.
title Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
title_short Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
title_full Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
title_fullStr Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
title_full_unstemmed Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
title_sort analysis of the phosphorus lone-pair orientational effect on 31p13c couplings in 7-(phosphamethyl)norbornene
publishDate 1988
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v164_n1-2_p1_Aucar
http://hdl.handle.net/20.500.12110/paper_01661280_v164_n1-2_p1_Aucar
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