Thermochemistry and thermolysis of sulphinic acid derivatives

Bujnicki, Bogdan; Mikołajczyk, M.; Omelańczuk, Jan

doi:10.1002/9780470772270.ch16

Cited by 3 publications

(1 citation statement)

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“…For the first time, we estimate that the S(O)−S(O) bond strength in acyclic vic -disulfoxides is on the order of 20 kcal mol -1 . To put this in context, we illustrate several representative S−S bond strengths in Scheme . − Clearly, oxidation of a sulfenyl sulfur to sulfinyl weakens the S−S bond considerably. An interesting feature, however, is that the first oxidation of a disulfide weakens the bond by ∼27 kcal mol -1 .…”

Section: Discussionmentioning

confidence: 99%

Computational Investigation of Vicinal Disulfoxides and Other Sulfinyl Radical Dimers

Gregory

Jenks

2003

J. Phys. Chem. A

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The structure and energetics of the simplest Vic-disulfoxide CH 3 S(O)S(O)CH 3 and its key isomers are reported. Computational methods include a CASSCF[2,2] treatment with a large basis set on sulfur and oxygen, followed by multireference MP2 refinement, and also the hybrid density functional B3LYP. Calculations at the G3 level were also carried out. In contrast to previous reports, a weak bond does exist for both Vic-disulfoxide diastereomers. A bond enthalpy near 20 kcal mol -1 is reported. The isomeric sulfenylsulfinate is slightly lower in energy than the Vic-disulfoxide. The B3LYP structure obtained for 5,5-di-t-butyltetrathiolane-2,3dioxide reproduces the essential structural parameters of the one experimentally known Vic-disulfinyl compound, 5-(1-adamantyl)-5-tert-butyltetrathiolane-2,3-dioxide.

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Section: Discussionmentioning

confidence: 99%