Spectra of aryldiazonium chlorides and the structure of diazonium cations
The structure of aryldiazonium cations was discussed, bringing in methods of IR and UV spectroscopy, x-ray diffraction study, and the MO LCAO method.
Both solid aryldiazoniums and their solutions are characterized by the presence of a triple bond in the diazonium group and a positive charge localized on both nitrogen atoms.
A difference of the UV spectra of the ortho- and meta-isomers from the spectra of the para-isomers was demonstrated for aryldiazonium cations.
The influence of the nature of the substituent upon the UV spectra of the aryldiazonium cations was investigated, and it was shown that the basic absorption band in the spectra of phenyldiazonium cations experiences a bathochromic shift with increasing electron-donor strength of the substituent in aryldiazonium cations.
It was shown by the MO LCAO method that the nature of the diazonium group (the presence of a triple bond and a delocalized positive charge on the two nitrogen atoms) is retained when any substituent is introduced, including the dimethylamino group.
KeywordsNitrogen Atom Positive Charge Diffraction Study Dimethylamino Bathochromic Shift
Unable to display preview. Download preview PDF.
- 1.L. A. Kazitsyna, S. V. Pasynkevich, and O. A. Reutov, Dokl. AN SSSR,141, 624 (1961); L. A. Kazitsyna, S. V. Pasynkevich, A. V. Kuznetsova, and O. A. Reutov, Izv. AN SSSR, Otd. Khim. N.,1962, 448, 1762; L. A. Kazitsyna, N. B. Kupletskaya, V. A. Ptitsyna, and O. A. Reutov, Zh. Obshch. Khimii,33, 3243 (1963).Google Scholar
- 2.Chr. Røming, Acta chem. scand.,17, 1444 (1963); O. Andersen and Chr. Røming, Acta chem. scand.,16, 1882 (1962).Google Scholar
- 3.Chr. Røming and K. Werstad, Chem. Commun.,14, 299 (1965).Google Scholar
- 4.T. N. Polynova, N. G. Bokii, M. A. Porai-Koshits, B. S. Kikot', and L. A. Kazitsyna, Zh. Struktur. Khimi,4, 453 (1963).Google Scholar
- 5.T. N. Polynova, Ya. Nesterova, M. A. Porai-Koshits, A. V. Kuznetsova, and L. A. Kazitsyna, Zh. Struktur. Khimii,7, 129 (1966).Google Scholar
- 6.L. A. Kazitsyna, O. A. Reutov, and Z. F. Buchkovskii, Zh. Fiz. Khimii,34, 850 (1960); M. Aroney, R. J. W. LeFevre, and R. L. Werner, J. Chem. Soc.,1955, 276; K. B. Whetsell, G. F. Hawkins, and F. E. Johnson, J. Amer. Chem. Soc.,78, 3360 (1956).Google Scholar
- 7.T. N. Polynova, N. G. Bokii, and M. A. Porai-Koshits, Zh. Struktur. Khimii,6, 878 (1965).Google Scholar
- 8.K. Klusins and M. Hoch, Helv. chim. acta,33, 2122 (1950).Google Scholar
- 9.P. F. Holt and B. J. Bullock, J. Chem. Soc.,1950, 2310.Google Scholar
- 10.A. Hantzsch and B. Hirsch, Ber.,29, 947 (1896); E. S. Lewis and H. Suhr, J. Amer. Chem. Soc.,82, 862 (1960); A. Hantzsch and J. S. Smithe, Ber.,33, 505 (1900); A. Hantzsch, Ber.,30, 2334 (1897);36, 2069 (1903).Google Scholar
- 11.H. A. G. Schoutissen, J. Amer. Chem. Soc.,55, 4541 (1953).Google Scholar
- 12.B. A. Bolto, M. Liveris, and J. Miller, J. Chem. Soc.,1956, 750.Google Scholar
- 13.Ch. N. R. Rao, Electronic Spectra in Chemistry [Russian translation], IL (1964).Google Scholar
- 14.L. A. Kazitsyna, L. D. Ashkinadze, and O. A. Reutov, Izv. AN SSSR, Ser. Khim.,1967, 702.Google Scholar
- 15.A. Kiss and G. Horvath, Acta chim. Acad. scient. hung.,39, 39 (1963);42, 15 (1964).Google Scholar
- 16.K. Zollinger, Chemistry of Azo-Dyes [Russian translation], IL (1964).Google Scholar
- 17.L. C. Anderson and J. W. Steedly, J. Amer. Chem. Soc.,76, 5144 (1954); L. C. Anderson and B. Manning, J. Amer. Chem. Soc.,77, 3018 (1955).Google Scholar
- 18.E. Knoevenagel, Ber.,23, 2995 (1890).Google Scholar
- 19.V. M. Rodionov, B. M. Bogoslovskii, and A. M. Fedorova, Laboratory Manual on the Chemistry of Intermediates and Dyes [in Russian], Goskhimizdat (1948), p. 42.Google Scholar