Abstract
The three isomeric cresols were subjected to the all-valence-electron CNDO/2 andPPP-CI calculations. Results from this study were used:
-
(i)
to compare the electronic structures of these isomers vis-à-vis parent compounds—phenol and toluene,
-
(ii)
to obtain a quantitative picture of their chemical reactivities and electronic absorption spectra.
Using the σ-core charges derived from CNDO/2 calculations and subsequently revising the valence-state ionisation potential and one-center-two-electron repulsion integrals, thePPP-CI calculations were performed on the title compounds according toNishimoto andForster scheme. In these calculations the pseudo-unsaturated nature of the methyl group has been given due consideration. In spectral assignment, compared to the conventionalPPP approach, the CNDO/2-basedPPP-CI method gave a better agreement with the experimental data.
Zusammenfassung
Drei isomere Kresole wurden mittels CNDO/2- undPPP-CI-Methoden untersucht; die Ergebnisse wurden bei den folgenden Untersuchungen benutzt:
-
(i)
Vergleich der elektronischen Strukturen dieser Verbindungen in bezug auf die Stammverbindungen Phenol und Toluol,
-
(ii)
eine quantitative Aussage über ihre chemischen Reaktivitäten und die Absorptionsspektren.
Mit Hilfe von CNDO/2 abgeleiteten σ-Ladungswerten, dem daraus ermittelten Valenz-Ionisations-Potential und Ein-Zentrum-zwei-Elektronen-Integralen wurden diePPP-CI-Berechnungen nach dem Schema vonNishimoto undForster ausgeführt. Die pseudo-ungesättigte Rolle der Methylgruppe wurde berücksichtigt. Im Gegensatz zurPPP-Näherung zeigte die auf CNDO/2 bezogenePPP-CI-Methode bei den Berechnungen der Spektren eine bessere Übereinstimmung mit den experimentellen Daten.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Topsom R. D., Prog. Phys. Org. Chem.12, 1 (1976).
Ehrenson S., Brownlee R. T. C., Taft R. W., Prog. Phys. Org. Chem.10, 1 (1973).
Nishimoto K., Forster L. S., Theoret. Chim. Acta4, 155 (1966).
Bailey M. L., Theoret. Chim. Acta13, 56 (1969).
Danihel I., Kuthan J., Coll. Czech. Chem. Comm.44, 873 (1979).
Gordon M. D., Neumer J. F., J. Phys. Chem.78, 1868 (1974).
Pople J. A., Proc. Phys. Soc. Ser. A1955, 69, 81.
Dietrich S. W., Jorgensen E. C., Kollmann P. A., Rothenberg R., J. Amer. Chem. Soc.98, 8310 (1976).
Allinger N. L., Maul J. J., Hickey M. J., J. Org. Chem.36, 2747 (1971).
Kudchadker S. A., Wilholt R. C., Zwolinski B. J., J. Phys. Chem.82, 245 (1978).
Pullmann B., Quantum Mechanics of Molecular Conformations London: J. Wiley. 1976.
Brownlee R. T. C., Taft R. W., J. Amer. Chem. Soc.92, 7007 (1970).
Dobas I., Eichler J., Coll. Czech. Chem. Comm.38, 2602 (1973).
Campbell A. N., Friesen R. J., Canad. J. Chem.37, 1296 (1959).
Dearden J. C., Forbes W. F., ibid.38, 897 (1960).
Kammerer H., Hewenz W., Spectrochim. Acta24A, 2059 (1968).
Ito M., J. Mole. Spectroscopy4, 134 (1960).
Pople J. A., Trans. Faraday Soc.49, 1375 (1953).
Pariser R., Parr R. G., J. Chem. Phys.21, 466, 767 (1953).
Namboodiri K. P. K.,Viswanathan S.,Ganesan R.,Bhasu V. C. J., J. Comp. Chem., in press.
Bhasu V. C. J., Sathyanarayana D. N., Phosphorus and Sulfur8, 171 (1980).
Bhasu V. C. J., Ph. D. Thesis, Indian Institute of Science, Bangalore, India, 1977.
Brownlee R. T. C., Taft R. W., J. Amer. Chem. Soc.90, 6537 (1968).
Platt J. R., Systematics of the Electronic Spectra of Conjugated Molecules, Paper No. 32. New York: Wiley. 1964.
Pople J. A., Beveridge D. L., Approximate Molecular Orbital Theory, appendix-program. New York: McGraw-Hill. 1970.
Nishimoto K., Forster L. S., Theor. Chim. Acta3, 407 (1965).
Nishimoto K., Mataga N., Z. Physik. Chem. (Frankfurt am Main)12, 335 (1957).
Fabian J., Tetrahedron29, 2449 (1973).
Dewar M. J. S., Morita T., J. Amer. Chem. Soc.91, 796 (1969).
Zahradnik R., Tesarova I., Pancir J., Coll. Czech. Chem. Comm.36, 2867 (1971).
Vogel A. I., A Text Book of Practical Organic Chemistry, pp. 169, 614, 677. London: E.L.B.S. 1968.
Hehre W. J., Radom L., Pople J. A., J. Amer. Chem. Soc.94, 1496 (1972).
Namboodiri K. P. K.,Viswanathan S.,Ganesan R.,Bhasu V. C. J., in preparation.
McClellan A. L., Tables of Experimental Dipole Moment, Vol. I. San Francisco: Freeman. 1963; Vol. II. California: Arhara Enterprises. 1974.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Krishnan Namboodiri, K.P., Viswanathan, S., Ganesan, R. et al. Cresols—An investigation into their electronic structure and spectra. Monatsh Chem 113, 949–963 (1982). https://doi.org/10.1007/BF00799236
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00799236