Thioether Thiol

Thiols add to alkenes under photochemical conditions to form thioethers, and the reaction can be done intramolecularly to give cyclic thioethers. Thiols also add to alkynes and with a palladium catalyst, vinyl sulfides can be formed. " Selenium compounds (RSeH) add in a similar manner. ... 

Complexes with thioether and mixed thioether/thiol ligands 326... 

S-oxidation. Aromatic and aliphatic sulfides, thioethers, thiols, thioamides, and thiocarba-mates may undergo oxidation to form sulfoxides and then, after further oxidation, sulfones (Fig. 4.23). 

Only a few hexadentate ligands have been reported (Scheme 12). They belong either to the thioether-thiol type or the Hahn type, in which 1,2-benzenedithiol units are connected through carboxylic acid amide bonds. 

The mixed thioether-thiol, HSCHjCH SMe, when treated with Pt(PPhj)3 forms the hydride, HPt(SCH2CH2SMe)(PPh3) in which both the thiolate and the thioether are coordinated to Pt. The compound HSCHjCHjSCHjCHjCHjSMe transforms Pt(PPh3)3 to yield HPt(SCH2CH2SCH2CHjCH2SMe)(PPh3), which has a four-coordinated, planar structure with the terminal thioether group uncoordinated. 

Reduction of gold(iii) to gold(i) or gold(o) is often observed in biological milieux. The reaction can be driven by naturally occurring reductants such as thioethers, thiols or even disulfides ... 

The desulfurization of organosulfur compounds with trivalent organophospho-rus compounds has been studied for more than four decades [118]. A variety of such reagents has been used to convert disulfides to monosulfides, trisulfides to disulfides or monosulfides, /3-keto sulfides to ketones, and sulfenimides to amines. They have also been used to remove sulfur from thioethers, thiols, and organometallic dithiocarboxylates, and oxygen from sulfones. 

The efficiency of the photoreaction is greater still in the presence of additional thioether-thiol. Even though these experiments relied on photoreactions (the biological process is thermal) to initiate the radical chemistry, it is interesting to observe the formation of methane concomitant with the disulfide. 

Laurence, C., Berthelot, M., Evain, K. and Illien, B. (2005) The pAThb scales and enthalpies of the hydrogen bond acceptor strength of thioethers, thiols, and disulfides. Can. J. Chem., 83, 138-145. 

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