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Abstract:

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.

Registro:

Documento: Artículo
Título:Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene
Autor:Aucar, G.A.; Giribet, C.G.; De Azúa, M.C.R.; Diz, A.C.; Contreras, R.H.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, 3600 Corrientes, Argentina
Departamento de Física, Facultad de Ciencias Exactas y Naturales, UBA, Ciudad Universitaria, Pab. 1, 1428 Buenos Aires, Argentina
Año:1988
Volumen:164
Número:1-2
Página de inicio:1
Página de fin:15
DOI: http://dx.doi.org/10.1016/0166-1280(88)80001-0
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v164_n1-2_p1_Aucar

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Citas:

---------- APA ----------
Aucar, G.A., Giribet, C.G., De Azúa, M.C.R., Diz, A.C. & Contreras, R.H. (1988) . Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene. Journal of Molecular Structure: THEOCHEM, 164(1-2), 1-15.
http://dx.doi.org/10.1016/0166-1280(88)80001-0
---------- CHICAGO ----------
Aucar, G.A., Giribet, C.G., De Azúa, M.C.R., Diz, A.C., Contreras, R.H. "Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene" . Journal of Molecular Structure: THEOCHEM 164, no. 1-2 (1988) : 1-15.
http://dx.doi.org/10.1016/0166-1280(88)80001-0
---------- MLA ----------
Aucar, G.A., Giribet, C.G., De Azúa, M.C.R., Diz, A.C., Contreras, R.H. "Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene" . Journal of Molecular Structure: THEOCHEM, vol. 164, no. 1-2, 1988, pp. 1-15.
http://dx.doi.org/10.1016/0166-1280(88)80001-0
---------- VANCOUVER ----------
Aucar, G.A., Giribet, C.G., De Azúa, M.C.R., Diz, A.C., Contreras, R.H. Analysis of the phosphorus lone-pair orientational effect on 31P13C couplings in 7-(phosphamethyl)norbornene. J. Mol. Struct. THEOCHEM. 1988;164(1-2):1-15.
http://dx.doi.org/10.1016/0166-1280(88)80001-0