THE SULFUR $K_\beta$ X-RAY EMISSION SPECTRA FROM THIOXANTHENE, THIANTHRENE, AND 10-THIOXANTHENONE
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Date
1975
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Ohio State University
Abstract
The molecular crystals, $C_{12}H_{10} S$ (thioxanthene), $C_{13}H_{8}S_{2}$ (thianthrene), and $C_{13}H_{8}SO$ (10-thioxanthenone), represent examples of a unique series of non-planar heterocyclic molecules, which are ``hinged” at the bridging-hetero atoms. It has been suggested that the sulfur atoms could use d-pi as well as p-pi orbitals and conjugation could occur despite the fact that the molecule is not $flat.^{1}$ Crystallographic work indicates that the $C-S$ and $C-C$ (central ring) distances are relatively insensitive to substitutions at the central carbon atom, which would suggest little, if any, pi interactions with the phenylene $groups.^{2}$ The sulfur $K_{\beta}$ X-ray photon emission spectra of these three compounds were run at a resolving power of about 1700 using a vertically oriented double-crystal X-ray $spectrometer.^{3}$ Generally speaking all the spectra indicate that the sulfur atoms are in an aromatic $environment.^{4}$ The spectral features are also sensitive to substitutions at the carbon atom opposite to the sulfur atom which would indicated conjugative interactions involving the sulfur 3p(pi) orbitals.
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$^{1}$ H. Lynton and E. G. Cox, J. Chem. Soc, 1956, 4886 (1956). $^{2}$ J. A. Gillean, D. W. Phelps, and A. W. Cordes, Acta Cryst, B29, 2296 (1973). $^{3}$H. C. Whitehead, J. D. Layfield, and G. Andermann, Rev. Sci. Instr. 43, 50 (1972). $^{4}$D. R. Phillips and G. Andermann, Physic. Fennica 9, Suppl. 51, 141 (1974) This work was supported by the National Science Foundation.
Author Institution: Department of Chemistry, University of Hawaii
Author Institution: Department of Chemistry, University of Hawaii