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Raman Spectra of Sulfur Dissolved in Primary Amines
I
Acknowledgments. Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, and to the Research Corporation for partial support of this research. I would also like to thank Dr. Z. I. Ariyan for his gift of two of the compounds used in this work. Acknowledgment is also made to Donna M. Olson and William S. Mullane, NSF undergraduate research participants, for technical assistance with certain parts of this study. References a n d Notes (1) (2) (3) (4)
Part I l l ; P. D. Sullivan, J. Phys. Chem.. 75, 2195 (1971). P. D. Sullivan, J. Phys. Chem.. 73, 2790 (1969). P. D. Sullivan, J Phys. Chem.. 74, 2563 (1970). Nomenclature follows the usual esr spectroscopists notation
~c-c--c-c-c i i i i
i
H H H H H f f P Y 6 6
(5) B. W. Ristow. Thesis. Cornell University. 1966. (6) W. F. Forbes and P. D. Sullivan, J. Amer. Chem. SOC.. 88, 2862 I~l q. R_R_I _ , .
(7) W. F. Forbes, P. D. Sullivan, and H. M. Wang, J. Amer. Chem. SOC.. 89, 2705 (1967). (8) That is, @ t othe oxygen atom. (9) W. F. Forbesand P. D. Sullivan, J. Chem. Phys., 48, 1411 (1968). (10) . , E. W. Stone and A. H. Maki, J. Chem. Phys.. . . 37.. 1326 (1962): . . 38.. 1254 (1963). (11) D. M. Geske, Progr. Phys. Org. Chem., 4, 125 (1967). (12) W. J.'Van den Hoek, Thesis, Technische Hogeschooi Delft, Hoiland, 1972. (13) N. M. Atherton, A. J. Blackhurst, and I. P. Cook, Trans. Faraday SOC.. 67, 2510 (1971). (14) M.D. Sevilla and G. Vincow. J. Phys. Chem., 72,3647 (1968).
(15) M. K. Carter and G. Vincow, J . Chem. Phys.. 47, 302 (1967). (16) R. W. Fessenden, J. Chim. Phys.. 61, 1570 (1964). (17) P. J. Krusic, P. Meakin. and J. P. Jesson, J. Phys. Chem.. 75, 3438 (1971). (18) P. J. Krusicand J. K. Kochi, J. Amer. Chem. Soc.. 93, 846 (1971). (19) N. L. Bauld. J. D. McDermod, C. E. Hudson, Y. S. Rim, J. Zoeiler, R. D. Gordon, and J. S. Hyde, J. Amer. Chem. SOC.. 91, 6666 (1969). (20) D. J. Edge and J. K. Kochi, J. Amer. Chem. SOC..94,7695 (1972). (21) W. F. Forbesand P. D. Sullivan. Can. J. Chem.. 46,317 (1968). (22) D. M. Geske and M. V. Merritt, J. Amer. Chem. SOC..91, 6921 (1969). (23) K. Scheffler, Ber. Bunsenges. Phys. Chem.. 65, 439 (1961). (24) L. M. Stock and P. E. Young, J. Amer. Chem. SOC.. 94, 7686 (1972). (25) J. Pilar, J. Phys. Chem.. 74, 4029 (1970). (26) C. Trapp, C. A. Tyson, and G. Giacometti, J. Amer. Chem, SOC.. 90, 1394 (1968). (27) P. D. Sullivan, J. Phys. Chem.. 76, 3943 (1972). (28) P. D. Sullivan, unpublished results. (29) J. K. Kochi and P. J. Krusic, J. Amer. Chem. SOC..91, 3940 (1969). (30) B. C. Gilbert, R. H. Schlossei, and W. M. Gulick, J. Amer. Chem. SOC..92, 2974 (1970). (31) D. Bachmann, 2. Phys. Chem.. 43, 198 (1964). (32) R. M. Dessau and S. Shih, J. Chem. Phys.. 57, 1200 (1972). (33) C-H = 1.08 A, C-0 = 1.36 A, 0-H = 0.98 A, LCOC = 120'. c-C = 1.54 A. (34) A. Hudson and K. D. J. Root, Tetrahedron. 25, 5311 (1969). (35). P. D. Sullivan, J. R. Bolton, and W. E. Geiger, J. Amer. Chem. Soc., 92, 4176 (1970). (36) This contribution is also probably angular dependent, but since only averaged values of the d splittings are being considered we have not calculated this angular dependence. (37) The values of Q c Y - ~ are, perhaps, somewhat surprisingly negative. The -/-ethoxy protons are of course 6 to the carbon atom and caiculations on simple hydrocarbons would have indicated a small positive value for a d proton. Therefore, the influence of the intervening oxygen atom must be sufficient to change the sign of this interaction.
Raman Spectra of Sulfur Dissolved in Primary Amines Francis P. Daly and Chris W. Brown* Department of Chemistry, University of Rhode Island, Kingston, Rhode Island 02881 (Received April 76, 1973)
Raman spectra of rhombic sulfur dissolved in ethylenediamine, n-propylamine, and monomethylamine have been measured. Bands due to new species are observed at 400,440,462, -510, and 535 cm-l. The band at 535 cm-1 is assigned to the symmetric stretching vibration of S3-. The antisymmetric stretching vibration of S3- is observed a t 585 cm-1 in the infrared spectrum of sulfur dissolved in ethylenediamine. The other new bands in the Raman spectra are attributed to polysulfides. The Raman spectrum of the ethylenediamine solution changed considerably during a 24-hr time dependence study, whereas the spectra of the other solutions changed only slightly.
Introduction Solutions of alkali metals and sulfur in liquid ammonia and amines have been the subject of numerous investigations for the better part of this century.1 The solutions are characterized by unusual colors and high conductivities; however, the exact nature of the solvent or solute is far from being understood. Recently, Smith and Koehler2 investigated the Raman spectra of alkali metals dissolved in liquid ammonia. We have been performing similar experiments using sulfur as a solute and herein we report on the Raman spectra of sulfur dissolved in three primary amines.
Experimental Section Rhombic sulfur (Alfa Inorganics, 99.999%) and monoethylamine (Matheson) were used without further purification. Ethylenediamine (EDA) and n-propylamine (both from Matheson Coleman and Bell) were distilled under atmospheric conditions and then under vacuum prior to being used. Raman spectra were measured using a Spex Industries Model 1401 double monochromator with photon counting detection and a C.R.L. Model 52-A argon ion laser emitting at 5145 A (1150 mW power at the sample). All spectra were measured with a spectral slitwidth
