The structures of hydrogen persulfide (HSSH, 18) and its monoxide (HS(O)SH, 3), dioxides (HS02SH, I, HS(0)S(0)H, 2), and tetraoxide (HS02S02H, 17) derivatives were examined by ab initio molecular orbital calculations at the HF/3-21G* and 6-31G* levels. The energetics of the rearrangement of a-disulfoxides (2) to thiosulfonates (1) via sulfenyl sulfinate (HS(O)OSH, 11), sulfinyl radical, thiyl radical, and/or sulfonyl radical were investigated. The calculated relative energies agree with proposed mechanisms and experimental results.
The 'H NMR and 13C NMR spectra of neopentyl and benzyl substituted disulfides, thiosulfinates, thiosulfonates, thiols, sulfides, sulfinic acids and sulfonic acids are reported. The deshielding electron withdrawing effects of -SO, -SO,, -SOz-, -SO,H, -SO,-, S 0 , H and S03CH3 on or-ðylene and benzylic protons are observed. The 'H NMR spectra show, except for two dialkylthiosulfinates, that the a'-protons of thiosulfinates absorb farther downfield than those of the thiosulfonates. Although the "C NMR spectra show that orso effects are deshielding and are smaller than the aso, effects, the aso values are more shielding than the ago, values for some compounds. The effects on 13C NMR spectra which result from substituting a phenyl group for a neopentyl or benzyl group are discussed. The or-methylene carbon shifts for neopentanesulfinic acid and or-toluenesulfinic acid are further downfield than those for the corresponding sulfonic acids.
C NMR spectra of thiols, sulfinic acids, sulfinyl chlorides, sulfoNc acids and sulfonic anhydrides have been obtained. The data are discussed in terms of the additivity of the deshielding effects exerted by the sulfur functionality at the a-or &position, and the shielding effects produced by the sulfur function at the y -position.
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