Abstract
The calculation of the transformation matrix between the molecular orbitals of the transition state and the educt provides detailed information on the alteration and interaction of the MO’s along the reaction coordinate. This is demonstrated for four different kinds of reactions: (a) Conrotatory ringopening of cyclobutene; (b) Addition of methylene to ethylene; (c) Nucleophilic substitution of CH3CN and CH3NC by CN−; (d) 1,2 Rearrangement of methylcarbene to ethylene. MNDO has been employed for the calculations but any other method may be used as well.
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Fukui, K., Fujimoto, H.: Bull. Chem. Soc. Japan41, 1989 (1968)
Fukui, K., Fujimoto, H.: Bull. Chem. Soc. Japan42, 3399 (1969)
Fukui, K.: Theory of orientation and stereoselection. Berlin: Springer-Verlag, 1975
Fleming, I.: Frontier orbitals and organic chemical reactions. New York: Wiley, 1976
Berson, J. A., Salem, L.: J. Am. Chem. Soc.94, 8917 (1972)
Epiotis, N. D.: Theory of organic reactions. Berlin: Springer-Verlag, 1978
Frenking, G.: J. Mol. Struct. THEOCHEM104, 233 (1983)
Dewar, M. J. S., Thiel, W.: J. Am. Chem. Soc.99, 4899 (1977)
McIver, Jr., J. W., Komornicki, A.: Chem. Phys. Letters10, 303 (1971);
Poppinger, D.: Chem. Phys. Letters35, 550 (1975)
Dewar, M. J. S., Kirschner, S.: J. Am. Chem. Soc.93, 4290 (1971)
McIver, Jr., J. W., Komornicki, A.: J. Am. Chem. Soc.94, 2625 (1972)
Stephenson, L. M., Brauman, J. I.: Acc. Chem. Res.7, 65 (1974)
Dewar, M. J. S., Haselbach, E.: J. Am. Chem. Soc.92, 590 (1970)
Ref. 4, p. 103f.
Rondan, N., Houk, K. N., Moss, R. A.: J. Am. Chem. Soc.102, 1770 (1980);
Zurawski, B., Kutzelnigg, W.: J. Am. Chem. Soc.100, 2654 (1978)
Bodor, N., Dewar, M. J. S., Wasson, J. S.: J. Am. Chem. Soc.94, 9095 (1972);
Schoeller, W. W., Aktekin, N.: J. Chem. Soc. Chem. Comm. 20 (1982)
Frenking, G., Schwarz, H.: Z. Naturforsch.36b, 797 (1981)
Ref. 4, p. 96.
Fujimoto, H., Yamabe, S., Fukui, K.: Tetrahedron Letters 439 (1971)
Salem, L.: J. Am. Chem. Soc.90, 543 (1968);
Klopman, G.: J. Am. Chem. Soc.90, 223 (1968);
Pearson, R. G.: J. Am. Chem. Soc.85, 3533 (1963);
Pearson, R., Songstad, J.: J. Am. Chem. Soc.89, 1827 (1967)
Ref. 4, p. 40f
Jones, W. M.: Rearrangements in ground and excited states. P. deMayo (ed.), Vol. 1, Essay 3. New York: Academic Press, 1980
Altmann, J. A., Csizmadia, I. G., Yates, K.: J. Am. Chem. Soc.97, 5217 (1975)
Frenking, G., Schmidt, J.: Tetrahedron, in press
Hammond, G. S.: J. Am. Chem. Soc.77, 334 (1955)
Raghavachari, K., Frisch, M.J., Pople, J. A., Schleyer, P. v. R.: Chem. Phys. Letters85, 145 (1982)
Keller, E.: Chem. unserer Zeit14, 56 (1980)
Jorgensen, W. L., Salem, L.: Orbitale organischer Moleküle. Weinheim: Verlag Chemie, 1974
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Frenking, G., Heinrich, N. Transformation matrices as tool to investigate the changes in the electronic structure of reacting molecules along the reaction coordinate. Theoret. Chim. Acta 65, 65–76 (1984). https://doi.org/10.1007/BF02427581
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DOI: https://doi.org/10.1007/BF02427581