The 2980 A Absorption Spectrum of 1,2,5-Selenadiazole

A. W. RICHARDSON
Chemistry Department, Bishop's University, Lennoxville, Quebec Received March 30, 1973

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The U.V. absorption spectrum of I ,2,5-selenadiazole in the 305G2600 A region has been recorded and, by analogy to previous studies of furazan (1,2,5-oxadiazole) and 1,2,5-thiadiazole, an interpretation of the spectrum in terms of an allowed electronic transition involving primarily activity of v5, a symmetric ring in-plane bending vibration, and vlo, a ring out-of-plane bending vibration, has been made. This analysis indicates that the excited state is non-planar, and the barrier t o planarity has been calculated t o be in the order of 115 cnl-I. Le spectre d'absorption U.V.du selena-1,2,5 diazole dans la region de 3050 a 2600 A a CtC enregistre. Par analogie avec des etudes anterieures sur le furazane (oxa-1,2,5 diazole) et sur le thia-1,2,5 diazole, on a interprkte le spectre en fonction d'une transition Clectronique permise impliquant surtout I'activitt de v,, une vibration symetrique de deformation du cycle dans le plan, et de vlo, une vibration de deformation du cycle hors du plan. Cette analyse a montrk que I'Ctat excitC est non-planaire; la barritre a la [Traduit par le journal] plankite a ete tvaluee a environ 115 cm-'.
Can. J. Chem., 52, 100 (1974)

Introduction We have recentlv re~ortedthe results of our investigations of the first U.V. absorption spectra of furazan (1,2,5-oxadiazole) (1) and 1,2,5thiadiazole (2). In both cases, analysis of the U.V. spectrum shows that the electronic transition is from a planar ground state to a non-planar excited state and that the barrier to planarity in the excited state is relatively small, being in the order of 215 cm-' for furazan and 460 cm-' for 1,2,5-thiadiazole. The investigation of the U.V. absorption spectrum of 1,2,5-selenadiazole was undertaken in order to extend the series of molecules studied.
d .

vapor at a fixed pressure but heated to about 75 "C by wrapping the absorption cell with heating tapes.

Observations The absorption spectrum of 1,2,5-selenadiazole vapor in the 3100-2700A region as recorded on a Cary model 14 spectrophotometer is shown in Fig. 1. The diffuseness of the spectrum is apparent from this tracing and was verified by higher resolution spectra recorded on the Jarrell-Ash 0.5 m spectrometer. The measured wavenumbers of the maxima of the vibronic bands listed in Table 1 were taken

Experimental
1,2,5-Selenadiazole was prepared by the reaction of ethylenediamine with SeOz in dimethylformamide (3). The product was first separated by steam distillation, then extracted into pentane, and concentrated. Final purification was effected by g.1.c. using a 20 ft x f in. column of 30% SE 30 on 45/60 Chrom W with a Varian Aerograph autoprep 700 gas chromatograph. Because of the low yield of the reaction and difficulties of purification, the purity of the compound was not as good as desired, but was, nevertheless, in excess of 95%. Low resolution spectra of 1,2,5-selenadiazole vapor in a 10 cm cell were recorded on a Cary model 14 spectrometer. Higher resolution spectra were recorded photoelectrically on a Jarrell-Ash 0.5 m spectrometer equipped with a photomultiplier using a 150 W d.c. xenon lamp as a source. For the latter studies, an excess of 1,2,5-selenadiazole was kept in a 1 m fused silica absorption cell with a side arm and the vapor pressure of the sample was controlled by varying the temperature of a slush bath o n the side arm. Some spectra were also recorded with the

FIG. 1. Ultraviolet absorption spectrum of 1,2,5selenadiazole vapor a t room temperature as recorded o n the Cary model 14 spectrophotometer. Only the pressure of sample in the cell was changed between the two traces.

RICHARDSON: ABSORPTION SPECTRUM O F I,2,5-SELENADIAZOLE

101

TABLE 1. Observed bands in the 2980 A absorption spectrum of 1,2,5-selenadiazole (Jarrell-Ash measurements)

Vobs (cm- I )

Assignment*

VCaNcd.(cm-')$

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K : : ..

*A u'-u"

transitLon in the Kth normal mode is labelled

=

$Frequencies calculated using v," = 1005 cm-1, v," 726 cm-', VLO" = 438 cm-I (5). v,' = 605 cm-'.

from traces obtained with the Jarrell-Ash spectrometer and are the averages of about 10 measurements, except for the very weak bands for which only 3 measurements were made. Due to the diffuseness of the bands, the uncertainty in the -:erage values listed is about +8 cm-'.

Table 1. The wavenumbers of the hot bands calculated using the vapor phase i.r. values of v," = 726 and v," = 1005 cm-' (5) agree with the observed wavenumbers within experimental error. As was done for furazan (1) and 1,2,5-thiadiazole (2), the Go'(vlo') term values were calculated from the observed U.V. wavenumbers and the i.r. value of v,," = 438 cm-' and fitted to a double minimum potential function (6). For 1,2,5-selenadiazole, it was not possible to carry out this fitting very accurately since the data are not too accurate and there are only four pieces of data to be used with the potential function which contains three parameters. From a number of calculations which were made, it is possible to conclude that the barrier to planarity in the excited state is in the order of 115 cm-'; however, the uncertainty in this value is rather large, being 30 cm-' at least.

Analysis Investigation of the microwave spectrum of 1,2,5-selenadiazole has shown that the spectrum is compatible with the molecule being planar with C,, symmetry as expected (4). Similarly, the i.r. and Raman spectra have been interpreted in terms of a planar C2, structure and assignments made for all 15 normal modes of vibration (5). By analogy to the analyses of the U.V. absorption spectra of furazan (1) and 1,2,5-thiadiazole (2), the bands in the U.V. spectrum of 1,2,5selenadiazole have been assigned as shown in

The author thanks the National Research Council of Canada and the Crabtree Fund of Bishop's University for financial support of this work, and Dr. J. C. D. Brand and the Chemistry Department of the University of Western Ontario for use of the Jarrell-Ash and Cary spectrophotometers. Mr. T. England prepared the sample of 1,2,5-selenadiazole and recorded most of the spectra used in the present analysis.

and A. W. RICHARDSON. Can. J . Chem. 1. B. J. FORREST 50, 2088 (1972). 2. E. FIRKINS and A . W. RICHARDSON. Chem. Commun. 1368 (1971). 3. V. BERTINI. Angew. Chem. Int. Ed. 6 , 563 (1967). 4. G. L . BLACKMAN, R. D. BROWN, F. R. BURDEN, and J. E. KENT.Chem. Phys. Lett. 1, 379 (1967). and I V. BERTINI. Spectrochim. Acta, 5. E. B E N E D E ~ 24A, 57 (1968). 6. J. B. COON, N. W. NAUGLE, and R. D. MCKENZIE. J. Mol. Spectrosc. 20, 107 (1966).