Artículo
Abstract:
In the present work, the relationship between the large substituent effects on 3J(C1H) in 1-X-3-M-bicyclo[1.1.1]pentanes, I, and the polarizability of the bridgehead C3 - Mα bond is investigated. The existence of such a relationship is suggested by the finding that the effect of an electronegative substituent X on 3J(C1Mα) couplings in I (M = H) is due to a distortion of the C3 - H bond toward the C1 center, which enhances the Fermi contact interaction. If such distortion originates in an electrostatic effect, then in other members of this series it can be expected that the substituent effects on 3J(C1 Mα) couplings should depend strongly on the C3 - Mα bond polarizability. Two approaches are followed. First, the ab initio CLOPPA-IPPP method is applied to study the C3 - Mα bond contribution to the molecular static polarizability tensor in I (M = H, F, CH3). Such bond polarizabilities are found to follow the same trend as calculated as well as experimentally determined substituent effects on 3J(C1Mα) couplings, which were measured as part of this work in I [X = H, Cl; M = F, CH3 and X = OCH3; M = Sn(CH3)3]. Second, 3J(C1Mα) couplings (M = H, CH3) are calculated at an ab initio level for X = H, F, and they are compared with those obtained in the parent compound (X = H) if the calculation is carried out in the presence of an inhomogeneous electric field. © 1998 John Wiley & Sons, Inc.
Registro:
| Documento: | Artículo |
| Título: | C3 - Mα bond contribution to polarizability tensor and 3J(C1Mα) NMR coupling constant in 1-X-3-M-bicyclo[1.1.1]pentanes |
| Autor: | Giribet, C.G.; Ruiz De Azúa, M.C.; Gómez, S.B.; Botek, E.L.; Contreras, R.H.; Adcock, W.; Della, E.W.; Krstic, A.R.; Lochert, I.J. |
| Filiación: | Departamento de Física, Universidad de Buenos Aires, Ciudad Universitaria, (1428) Buenos Aires, Argentina Department of Chemistry, Flinders University, Bedford Park, SA 5042, Australia Argentine National Research Council, Argentina SECyT (UNNE) |
| Palabras clave: | Bicyclo[1.1.1]pentanes; Bond polarizabilities; CLOPPA-IPPP; Localized orbitals; NMR coupling constants |
| Año: | 1998 |
| Volumen: | 19 |
| Número: | 2 |
| Página de inicio: | 181 |
| Página de fin: | 188 |
| DOI: | http://dx.doi.org/10.1002/(SICI)1096-987X(19980130)19:2<181::AID-JCC10>3.0.CO;2-L |
| Título revista: | Journal of Computational Chemistry |
| Título revista abreviado: | J. Comput. Chem. |
| ISSN: | 01928651 |
| CODEN: | JCCHD |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01928651_v19_n2_p181_Giribet |
Referencias:
- Della, E.W., Lochert, I.J., Peruchena, N.M., Aucar, G.A., Contreras, R.H., (1996) J. Phys. Org. Chem., 9, p. 168
- Engelmann, A.R., Contreras, R.H., (1983) Int. J. Quantum Chem., 23, p. 1033
- Diz, A.C., Ruiz De Azúa, M.C., Giribet, C.G., Contreras, R.H., (1990) Int. J. Quantum Chem., 37, p. 663
- Giribet, C.G., Demarco, M.D., Ruiz De Azúa, M.C., Contreras, R.H., (1997) Mol. Phys., 91, p. 105
- Lazzeretti, P., Zanasi, R., (1982) J. Chem. Phys., 77, p. 2448
- Lazzeretti, P., (1979) Int. J. Quantum Chem., 15, p. 181
- Lazzaretti, P., (1979) J. Chem. Phys., 71, p. 2514
- McCurdy, C.V., Rescigno, T.N., Yaeger, D.L., McKoy, V., (1977) Methods of Electronic Structure Theory, 3, p. 111. , H. F. Schaefer III, Ed., McGraw-Hill, New York
- Schmidt, M.W., Boatz, J.A., Baldridge, K.K., Koseki, S., Gordon, M.S., Elbert, S.T., Lam, B., (1987) QCPE Bull., 7, p. 115
- Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257
- Löwdin, P.O., (1962) J. Math. Phys., 3, p. 969
- Löwdin, P.O., (1965) Phys. Rev., A139, p. 357
- Ruiz De Azúa, M.C., Diz, A.C., Giribet, C.G., Contreras, R.H., Rae, I.D., (1986) Int. J. Quantum Chem., S20, p. 585
- Verwoerd, W.S., (1979) Chem. Phys., 44, p. 151
- Jorgensen, P., Simons, I., (1981) Second Quantization-Based Methods in Quantum Chemistry, , London, Academic Press, Ch. 6
- Wiberg, K.B., (1984) J. Comput. Chem., 5, p. 197
- Della, E.W., Cotsaris, E., Hine, P.T., Pigou, P.E., (1981) Aust. J. Chem., 34, p. 923
- Bennett, B., Raynes, W.T., Anderson, C.W., (1989) Spectrochim. Acta, 45 A, p. 821
- Hansen, P.E., (1981) Prog. NMR Spectrosc., 14, p. 175
- Amos, A.T., Crispin, R.J., (1975) J. Chem. Phys., 63, p. 189
- Adcock, W., Della, E.W., Lochert, I.J., Krstic, A.R., in preparation; Wrackmeyer, B., (1985) Ann. Rep. NMR Spectrosc., 16, p. 73
- Barfield, M., Canada Jr., E.D., McDaniel, C.R., Marshall, J.L., Walter, S.R., (1983) J. Am. Chem. Soc., 105, p. 3411
- Chiang, J.F., Bauer, S.H., (1970) J. Am. Chem. Soc., 92, p. 1614
- Chiang, J.F., (1971) J. Am. Chem. Soc., 93, p. 5044
- Barfield, M., Brown, S.E., Canada Jr., E.D., Ledford, N.D., Marshall, J.L., Walter, S.R., Yakali, E., (1980) J. Am. Chem. Soc., 102, p. 3355
- Barfield, M., Della, E.W., Pigou, P.E., (1984) J. Am. Chem. Soc., 106, p. 5051
- Aucar, G.A., Zunino, V., Ferraro, M.B., Giribet, C.G., Ruiz De Azúa, M.C., Contreras, R.H., (1990) J. Mol. Struct. (Theochem), 205, p. 63
- Della, E.W., Cotsaris, E., Hine, P.T., (1981) J. Am. Chem. Soc., 103, p. 4131
- Della, E.W., Head, N.J., (1995) J. Org. Chem., 60, p. 5303
- Eaton, P.E., (1992) Angew. Chem. Int. Ed. Engl., 31, p. 1421
Citas:
---------- APA ----------
Giribet, C.G., Ruiz De Azúa, M.C., Gómez, S.B., Botek, E.L., Contreras, R.H., Adcock, W., Della, E.W.,..., Lochert, I.J. (1998) . C3 - Mα bond contribution to polarizability tensor and 3J(C1Mα) NMR coupling constant in 1-X-3-M-bicyclo[1.1.1]pentanes. Journal of Computational Chemistry, 19(2), 181-188.http://dx.doi.org/10.1002/(SICI)1096-987X(19980130)19:2<181::AID-JCC10>3.0.CO;2-L
---------- CHICAGO ----------
Giribet, C.G., Ruiz De Azúa, M.C., Gómez, S.B., Botek, E.L., Contreras, R.H., Adcock, W., et al. "C3 - Mα bond contribution to polarizability tensor and 3J(C1Mα) NMR coupling constant in 1-X-3-M-bicyclo[1.1.1]pentanes" . Journal of Computational Chemistry 19, no. 2 (1998) : 181-188.http://dx.doi.org/10.1002/(SICI)1096-987X(19980130)19:2<181::AID-JCC10>3.0.CO;2-L
---------- MLA ----------
Giribet, C.G., Ruiz De Azúa, M.C., Gómez, S.B., Botek, E.L., Contreras, R.H., Adcock, W., et al. "C3 - Mα bond contribution to polarizability tensor and 3J(C1Mα) NMR coupling constant in 1-X-3-M-bicyclo[1.1.1]pentanes" . Journal of Computational Chemistry, vol. 19, no. 2, 1998, pp. 181-188.http://dx.doi.org/10.1002/(SICI)1096-987X(19980130)19:2<181::AID-JCC10>3.0.CO;2-L
---------- VANCOUVER ----------
Giribet, C.G., Ruiz De Azúa, M.C., Gómez, S.B., Botek, E.L., Contreras, R.H., Adcock, W., et al. C3 - Mα bond contribution to polarizability tensor and 3J(C1Mα) NMR coupling constant in 1-X-3-M-bicyclo[1.1.1]pentanes. J. Comput. Chem. 1998;19(2):181-188.http://dx.doi.org/10.1002/(SICI)1096-987X(19980130)19:2<181::AID-JCC10>3.0.CO;2-L
