Navegar

Colección

Datos Estadísticas

Artículo

El editor solo permite decargar el artículo en su versión post-print desde el repositorio. Por favor, si usted posee dicha versión, enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

Lithium dimethylamide (monomer and dimer) and several carbonyl complexes proposed as intermediates in its CO insertion reaction have been investigated by means of ab initio calculations (6-31+G//6-31G and MP2/6-31+G*//6-31G). The calculated values of the main geometrical parameters of the dimer are very close to those from solid-state determinations with stable lithium dialkylamides. The dimerization energy is predicted to be -60.7 and -59.9 kcal/mol at 6-31+G//6-31G and MP2/6-31+G*//6-31G levels, respectively. Calculations show a η2-coordinated lithium in the first intermediate derived from lithium dimethylamide monomers and CO and a rather long C-O bond (1.30 A). This indicates a significant alkoxycarbene character, rather than the classical carbamoyl structure. A second intermediate arising from a second CO insertion exhibits a planar geometry with relatively short O-Li bonds and the lithium atom coordinated to both oxygens. The calculations predict the double carbonylation to be a thermodynamically favorable process (-37.6 and 27.7 kcal/mol at 6-31+G and MP2/6-31+G* levels, respectively), in contrast to previous reports but in agreement with experimental results. A third intermediate, formally produced by the coupling of the two just described, shows two η2-coordinated lithiums and a planar arrangement of the main heavy atoms: the calculated high stability (-85.8 and -91.2 kcal/mol at 6-31+G//6-31G and MP2/6-31 +G*//6-31G levels, respectively), explains the high yields of substituted hydroxymalonamides obtained under special reaction conditions. The properties of the tetramethylurea dianion proposed as the precursor for dimethylformamides were also calculated: the high electron density (-1.113) found for the central carbon atom prodicts the facility of this intermediate for producing tetramethylureas. © 1994, American Chemical Society. All rights reserved.

Registro:

Documento: Artículo
Título:Theoretical Studies of Chemical Interactions. Ab Initio Calculations on Lithium Dialkylamides and Their Carbonylation Reactions
Autor:Viruela-Martin, P.; Viruela-Martin, R.; Tomás, F.; Nudelman, N.S.
Filiación:The Departamento de Quimica Fisica, Universidad de Valencia, C/Dr. Moliner, 50, 46100 Burjasot, Valencia, Spain
Departamento de Quimica Organica, Facultad de Ciencias Exactas, Universidad de Buenos Aires, Pab. II, P. 3, Ciudad Univ., 1428, Buenos Aires, Argentina
Año:1994
Volumen:116
Número:22
Página de inicio:10110
Página de fin:10116
DOI: http://dx.doi.org/10.1021/ja00101a032
Título revista:Journal of the American Chemical Society
Título revista abreviado:J. Am. Chem. Soc.
ISSN:00027863
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v116_n22_p10110_ViruelaMartin

Referencias:

  • Parshall, G.W., Homogeneous Catalysis (1980), Wiley-Interscience: New York; Keim, W., Catalysis in C1 Chemistry (1983), Riedel Pub.: Dordrecht; Lippard, S.J., (1991) Isr. J. Chem., 30, p. 331
  • Wolczanski, P.T., Bercaw, J.E., (1980) Acc. Chem. Res., 13, p. 121
  • Parshall, G.W., (1987) Organometallics, 6, p. 687
  • Marks, T.J., (1992) Acc. Chem. Res., 25, p. 57
  • Nalwa, H.S., (1991) App. Organomet. Chem., 5, p. 349
  • Botistini, A., Consiglio, G., (1992) Organometallics, 11, p. 1766
  • Knifton, K.F., Alexander, D.C., (1986) Isr. J. Chem., 27, p. 255
  • Knifton, K.F., (1983) J. Catal., 79, p. 147
  • Seyferth, D., Weinstein, R.M., Wang, W., Hui, R.C., Archer, C.M., (1984) Isr. J. Chem., 24, p. 167
  • Olah, G.A., (1987) Chem. Rev., 87, p. 671
  • Williams, G.D., Whittle, R.R., Geoffroy, G.L., Rheingold, R.L., (1987) J. Am. Chem. Soc., 109, p. 3936
  • Giannoccaro, P.J., (1987) Organomet. Chem., 336, p. 271
  • Ozawa, F., Soyana, H., Yanagihara, H., Aoyama, I., Takino, H., Izawa, K., Yamamoto, T., Yamamoto, A., (1985) J. Am. Chem. Soc., 107, p. 3235
  • Perez, D., Lewkovicz, E., Nudelman, N.S., (1990) Synthesis, p. 917
  • Perez, D., Nudelman, N.S., (1988) J. Org. Chem., 53, p. 408
  • Nudelman, N.S., Perez, D., (1983) J. Org. Chem., 48, p. 133
  • Lewkowicz, E., Furlong, J.P.J., Nudelman, N.S., (1991) Acta Phys. Org. Chem., p. 426. , (Brasil)
  • Seebach, D., (1990) Angew. Chem., Int. Ed. Engl., 29, p. 1320
  • Seebach, D., (1988) Angew. Chem., Int. Ed. Engl., 27, p. 1624
  • Poll, R., Seebach, D., (1989) J. Am. Chem. Soc., 111, p. 2622
  • Laube, T., Dunitz, J.D., Seebach, D., (1985) Helv. Chim. Acta, 68, p. 1373
  • Amstutz, R., Schweizer, W.B., Seebach, D., Dunitz, J.D., (1981) Helv. Chim, Acta, 64, p. 2617
  • Gregory, K., Schleyer, P.v.R., Snaith, R., (1991) Adv. Inorg. Chem., 37, p. 47
  • Setzer, W.N., Schleyer, P.v.R., (1985) Adv. Organomet. Chem., 24, p. 354
  • Mulvey, R.E., (1991) Chem. Soc. Rev., 20, p. 167
  • Clegg, W., MacGregor, M., Mulvey, R.E., O'Neil, P.A., (1992) Angew. Chem., 104, p. 74
  • (1992) Angew, Chem., Int. Ed. Engl., 31, p. 93
  • Armstrong, D.R., Barr, D., Clegg, W., Hodgson, S.M., Mulvey, R.E., Reed, D., Snaith, R., Wright, D.S., (1989) J. Am. Chem. Soc., 111, p. 4719
  • Barr, D., Clegg, W., Mulvey, R.E., Snaith, R., Wright, D.S., (1987) J. Chem. Soc., Chem. Commun., p. 716
  • Jackman, L.M., Chen, X., (1992) J. Am. Chem. Soc., 114, p. 403
  • Jackman, L.M., Rakiewicz, E.F., (1991) J. Am. Chem. Soc., 113, p. 1202
  • Jackman, L.M., Scarmoutzos, L.M., (1987) J. Am. Chem. Soc., 109, p. 5348
  • Jackman, L.M., Scarmoutzos, L.M., Smith, B.D., Williard, P.G., (1988) J. Am. Chem. Soc., 110, p. 6058
  • Barr, D., Berrisford, J., Jones, R.V.H., Slawin, A.M.Z., Snaith, R., Stoddart, J.F., Williams, D.J., (1989) Angew. Chem., Int. Ed. Engl., 28, p. 1044. , and references cited therein
  • Gilchrist, J.H., Collum, D.B., (1992) J. Am. Chem. Soc., 114, p. 794
  • Galiano-Roth, A.S., Michaelides, E.M., Collum, D.B., (1988) J. Am. Chem. Soc., 110, p. 2658
  • DePue, J.S., Collum, D.B., (1988) J. Am. Chem. Soc., 110, pp. 5518-5524
  • Nudelman, N.S., Lewkowicz, E., Furlong, J.P.J., (1993) J. Org. Chem., 58, p. 1847
  • Schleyer, P.v.R., (1990) Chem. Rev., 90, p. 1061. , and references cited therein
  • Kaufman, E., Schleyer, P.v.R., Houk, K.N., Wu, Y.-D., (1985) J. Am. Chem. Soc., 107, p. 5560
  • Kaufman, E., Schleyer, P.v.R., Gronert, S., Streitwieser, A., Jr., Halpern, M., (1987) J. Am. Chem. Soc., 109, p. 2553
  • Streitwieser, A., Jr., (1984) Acc. Chem. Res., 7, p. 353
  • Streitwieser, A., Jr., (1987) J. Am. Chem. Soc., 109, p. 1782
  • Barr, D., Berrisford, J., Mendez, L., Slawin, A.M.Z., Snaith, R., Stoddart, J.F., Williams, D.J., Wright, D.S., (1991) Angew. Chem., Int. Ed. Engl., 30, p. 82
  • Armstrong, D.R., Mulvey, R.E., Walker, G.T., Barr, D., Snaith, R., Clegg, W., Reed, D., (1988) J. Chem. Soc., Dalton Trans., p. 620
  • McKee, M.L., (1985) J. Am. Chem. Soc., 107, p. 7284
  • Romesberg, F.E., Collum, D.B., (1992) J. Am. Chem. Soc., 114, p. 2112
  • Hehre, W.J., Radom, L., Schleyer, P.R., Pople, J.A., Ab-Initio Molecular Orbital Theory (1986), Wiley: NY; Poppinger, D., (1975) Chem. Phys. Lett., 35, p. 550
  • Schlegel, M.B., (1982) J. Comput. Chem., 3, p. 214
  • Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257
  • Hariharan, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, p. 213
  • Gordon, M.S., (1980) Chem. Phys. Lett., 28, p. 213
  • Clark, T., Chandrasekhar, J., Spitznagel, G.W., Schleyer, P.v.R., (1983) J. Comput. Chem., 4, p. 294
  • Chandrasekhar, J., Andrade, J.G., Schleyer, P.v.R., (1981) J. Am. Chem. Soc., 103, p. 5609
  • Frisch, M.J., Pople, J.A., Binkley, J.S., (1984) J. Chem. Phys., 80, p. 3265
  • White, J.C., Cave, R.J., Davidson, E.R., (1988) J. Am. Chem. Soc., 110, p. 6308
  • Moller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618
  • Binkley, J.S., Pople, J.A., (1975) Int. J. Quantum Chem., 9, p. 229
  • Dewar, M.J.S., (1985) J. Am. Chem. Soc., 107, p. 3902
  • Dewar, M.J.S., Thiel, W., (1977) J. Am. Chem. Soc., 99, p. 4899
  • Engelhardt, L.M., May, R.E., Raston, C.L., White, A.H., (1978) J Chem. Soc., Dalton Trans., p. 1619
  • Galiano-Roth, A.S., Collum, D.B., (1989) J. Am. Chem. Soc., 111, p. 6772
  • Nudelman, N.S., Perez, D.G., (1989) J. Chem. Soc., p. 931. , Perkin Trans. 2
  • McKee, M.L., (1985) J. Am. Chem. Soc., 107, p. 859
  • Kaufman, E., Clark, T., Schleyer, P.v.R., (1984) J. Am. Chem. Soc., 106, p. 1856
  • Boche, G., Wagner, H.-U., (1984) J. Chem. Soc., Chem. Commun., p. 1591
  • Williard, P.G., Hintze, M.J., (1987) J. Am. Chem. Soc., 109, p. 5539
  • Nudelman, N.S., Doctorovich, F., Amorin, G., (1990) Tetrahedron Lett., p. 2533
  • Ozawa, F., (1984) Organometallics, 3, p. 683
  • Ozawa, F., Sagimoto, T., Yamamoto, T., Yamamoto, A., Organometallics, p. 692
  • Fagan, P.J., Manriquez, J.M., Marks, T.J., Day, V.W., Vollmer, S.H., Day, C.S., (1980) J. Am. Chem. Soc., 102, p. 5393
  • Francalanci, F., Gardano, A., Abis, L., Fiorani, T., Foa, M.J., (1983) Organomet. Chem., 243, p. 87
  • Evans, W.J., Wayda, A.L., Hunter, W.E., Atwood, J.L., (1981) J. Chem. Soc., Chem. Commun., p. 706
  • Casey, C.P., Andrews, M.A., McAlister, D.R., (1979) J. Am. Chem. Soc., 101, p. 3371
  • Nudelman, N.S., Perez, D., Galloy, J., Watson, W.H., (1983) Acta Crystallogr., C39, p. 393

Citas:

---------- APA ----------
Viruela-Martin, P., Viruela-Martin, R., Tomás, F. & Nudelman, N.S. (1994) . Theoretical Studies of Chemical Interactions. Ab Initio Calculations on Lithium Dialkylamides and Their Carbonylation Reactions. Journal of the American Chemical Society, 116(22), 10110-10116.
http://dx.doi.org/10.1021/ja00101a032
---------- CHICAGO ----------
Viruela-Martin, P., Viruela-Martin, R., Tomás, F., Nudelman, N.S. "Theoretical Studies of Chemical Interactions. Ab Initio Calculations on Lithium Dialkylamides and Their Carbonylation Reactions" . Journal of the American Chemical Society 116, no. 22 (1994) : 10110-10116.
http://dx.doi.org/10.1021/ja00101a032
---------- MLA ----------
Viruela-Martin, P., Viruela-Martin, R., Tomás, F., Nudelman, N.S. "Theoretical Studies of Chemical Interactions. Ab Initio Calculations on Lithium Dialkylamides and Their Carbonylation Reactions" . Journal of the American Chemical Society, vol. 116, no. 22, 1994, pp. 10110-10116.
http://dx.doi.org/10.1021/ja00101a032
---------- VANCOUVER ----------
Viruela-Martin, P., Viruela-Martin, R., Tomás, F., Nudelman, N.S. Theoretical Studies of Chemical Interactions. Ab Initio Calculations on Lithium Dialkylamides and Their Carbonylation Reactions. J. Am. Chem. Soc. 1994;116(22):10110-10116.
http://dx.doi.org/10.1021/ja00101a032