Abstract
The experimental values of the gas-phase proton affinities for a variety of 4-substituted benzonitriles, 4-substitutedN, N-dimethylanilines, and 4-substituted benzaldehydes have been examined by means of correlation analysis techniques and by ab initio quantum mechanical methods (MP2/ 6-31G(d) level). From this study it is concluded that in the gas phase, 4-(dimethylamino)-benzonitrile essentially protonates on the dimethylamino group, while protonated 4-cyanobenzaldehyde is very nearly a 2∶1 mixture of the carbonyl- and cyano-protonated forms.
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See, e.g.,Gas Phase Ion Chemistry; Bowers, M. T., Ed.; Academic Press: New York, 1979; Vols. 1, 2; 1984, Vol. 3.
Lias, S. G.; Liebman, J. F.; Levin, R. D.J. Chem. Phys. Ref. Data 1984,13, 695.
See, e.g.,Collision Spectroscopy; Cooks, R. G., Ed.; Plenum Press, New York, 1978.
See, e.g.,Similarity Models in Organic Chemistry, Biochemistry and Related Fields; Zalewski, R. I.; Krygowski, T. M.; Shorter, J., Eds.; Elsevier: Amsterdam, 1991.
Factor Analysis in Chemistry; Malinowski, E. R.; Howery, D. G.; R. E. Krieger; Malabar, FL, 1989.
Exner, O.Prog. Phys. Org. Chem. 1990,18, 129.
Correlation Analysis in Chemistry, Recent Advances; Chapman, N. B.; Shorter, J., Eds.; Plenum Press: New York, 1978.
Abboud, J.-L. M.; Herreros, M.; Notario, R.; Esseffar, O.; Yáñez, M.J. Am. Chem. Soc. 1996,118, 1126.
Notario, R.; Herreros, M.; El Hammadi, A.; Homan, H.; Abboud, J.-L. M.; Forfar, I.; Claramunt, R. M.; Elguero, J.J. Phys. Org. Chem. 1994,7, 657.
Abboud, J.-L. M.; Mó, O.; de Paz, J. L. G.; Yáñez, M.; Esseffar, M.; Bouab, W.; El-Mouhtadi, M.; Mokhlisse, R.; Ballesteros, E.; López-Mardomingo, C.; Notario, R.J. Am. Chem. Soc. 1993,115, 12468.
Abboud, J.-L. M.; Cabildo, P.; Cañada, T.; Catalán, J.; Claramunt, R. M.; de Paz, J. L. G.; Elguero, J.; Homan, H.; Notario, R.; Toiron, C.; Yranzo, G. I.J. Org. Chem. 1992,57, 3938.
Lehman, A. T.; Bursey, M. M.Ion Cyclotron Resonance Spectrometry; Wiley: New York, 1976.
Taft, R. W.; Topsom, R. D.Prog. Phys. Org. Chem. 1987,16, 1.
Hehre, W. J.; Ditchfield, R.; Pople, J. A.J. Chem. Phys. 1972,56, 2257.
MØller, C.; Plesset, M. S.Phys. Rev. 1934,46, 618.
Pople, J. A.; Scott, A. P.; Wong, M. W.; Radom, L.Isr. J. Chem. 1993,33, 345.
Gaussian 94. Revision B.3 computer program; M. J. Frisch, C. W. Trucks, H. B. Schlegel, D. M. W. Cill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andrés, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. González, J. A. Pople, Gaussian Inc., Pittsburgh, PA, 1995.
See, e.g., Pipeng, Y.J. Chem. Res. (S),1993, 368 and references therein.
McClellan, A. L.,Tables of Experimental Dipole Moments; Freeman: San Francisco, 1963.
Syrkin, Yu. K.; Dyatkina, M. E.Structure of Molecules and the Chemical Bond; Butterworths: London, 1950.
X-Ray data by Heine, A.; Herbst-Irmer, R.; Stalke, D.; Kühnle, W.; Zachariasse, K. A., as quoted in Ref. 17.
Kajimoto, O.; Yokohama, H.; Ooshima, Y.; Endo, Y.Chem. Phys. Lett. 1991,179, 455.
Serrano-Andrés, L. Merchán, M.; Roos, B. O.; Lindh, R.J. Am. Chem. Soc. 1995,117, 3189.
Berthelot, M.; Helbert, M.; Laurence, C.; Le Questel, J.-Y.; Anvia, F.; Taft, R. W.J. Chem. Soc., Perkin Trans. 2,1993, 625.
Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A.,Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986.
Abboud, J.-L. M.; Notario, R.; Bertrán, J.; Taft, R. W.J. Am. Chem. Soc. 1991,113, 4738.
Lewis, G. N.; Randall, M.Thermodynamics, 2nd Edition, revised by Pitzer, K. S.; Brewer, L.; McGraw Hill: New York, 1961; Chaps. 13–15.
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This work is dedicatedin memoriam to Professor Robert W. Taft.
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Castaño, O., Notario, R., Hori, K. et al. The site of protonation of bifunctional bases with competing basic centers. I. Aromatic nitriles. Struct Chem 7, 321–327 (1996). https://doi.org/10.1007/BF02275158
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DOI: https://doi.org/10.1007/BF02275158