60870-95-3Relevant academic research and scientific papers
CARBONYL SULFIDES AS POSSIBLE INTERMEDIATES IN THE PHOTOLYSIS OF OXATHIIRANES
Carlsen, Lars,Snyder, James P.,Holm, Arne,Pedersen, Erik
, p. 1257 - 1262 (1981)
Diphenyl oxathiirane, formed by irradiation of thiobenzophenone S-oxide at 77 K, is photochemically converted into a blue, thermally unstable compound which decomposes at ca 100-110 K (λmax 550 nm, (ε ca 11,000).Lack of change in magnetic susceptibility during the light induced conversion of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients.The unknown carbonyl sulfide functionality, R2C=O=S, thereby emerges as a strong candidate for producing the visible absorption.Comparison of the wave function for CH2=S=O and CH2=O=S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical.The failure to observe cycloaddition products between the blue species and several dipolarophiles is rationlized in terms of a labile carbonyl sulfide intermediate capable of facile sulfur extrusion from a long, weak O-S bond.Finally, the electronic absorption spectra of a series of para-substituted benzaldehyde O-sulfide model system have been calculated with CNDO/S-CI and correlated with the λmax's of the corresponding series of diaryl blue substrates.The sum of the available experimental and theoretical data is consistent with the existence of closed shell carbonyl sulfides as observable, though labile, intermediates from the photolysis of oxathinanes.
Photochemical formation and reactivities of substituted oxathiiranes in low-temperature argon matrices
Reisenauer, Hans Peter,Mloston, Grzegorz,Romanski, Jaroslaw,Schreiner, Peter R.
scheme or table, p. 6269 - 6275 (2011/12/02)
Thiocarbonyl S-oxides (sulfines) derived from aliphatic and cycloaliphatic thioketones were irradiated in argon matrices at 10 K, and the resulting oxathiiranes were identified by comparison of computed and experimental IR spectra. Upon photolysis at 10 K, depending on the substitution pattern, the oxathiiranes underwent either H-shift reactions or regioselective ring enlargements to form the corresponding thioesters. After warming of the matrix material to 38-40 K, the oxathiiranes underwent fast desulfurization to yield the corresponding ketones. Density functional theory (DFT) computations at the B3LYP/6-311+G(3df,3pd) level suggest that the desulfurizations of oxathiiranes occurred as bimolecular processes with activation enthalpies near 0 kcal mol-1.
