16601-12-0

New ferrocenylsulfonium cation based ionic liquids were prepared by direct alkylation of the corresponding ferrocenyl-based thioethers with N-alkylbis(trifluoromethanesulfonyl)imides (R′TFSI). This convenient direct access to organometallic sulfonium bis(trifluoromethanesulfonyl)imide (TFSI) salts without the need for ion exchange was chosen in order to obtain highly pure and reversibly redox active room temperature ILs in many cases. In other cases the anion cation interaction in the solid state was studied by XRD analyses. Moreover a diferrocenylmethylsulfonium tetrafluoroborate with two redox active centers was synthesized. The redox chemistry of these sulfonium salts was investigated via cyclic voltammetry. Furthermore, UV-Vis spectra and thermoanalytical data are discussed. The electron-withdrawing sulfonium group is directly bonded to the ferrocenyl unit, therefore this cationic group influences the potential of these ionic liquids in a more pronounced way than being anchored to the ferrocenyl unit via an organic spacer. With their low absorbance in the visible light and reversible, tunable redox potential, these room temperature ILs open perspectives as redox mediators in dye sensitized solar cells (DSSCs), as redox electrolytes in supercapacitors or as overcharge protection additives in batteries.

-

The reactions of p-toluenesulfinic acid (1) with dialkoxy disulfides (2), dialkoxy sulfides (6), diamino disulfides (8), diamino sulfides (9), and diamino sulfoxides (15), were examined and found to give di-p-toluenesulfonyl disulfide (3), di-p-toluenesulfonyl sulfide (4), amino p-toluenesulfonyl disulfides (10), amino p-toluenesulfonyl sulfides (13), and p-toluenesulfinamides (16), respectively.Keywords - sulfinate S-nucleophile; intermolecular reaction; dialkoxy disulfide; dialkoxy sulfide; diamino disulfide; diamino sulfide; diamino sulfoxide; amino sulfonyl disulfide; amino sulfonyl sulfide

The reactions of diamino disulfides (2) and diamino sulfides (3) with p-toluenesulfinic acid (1) were found to give new types of compounds, amino p-toluenesulfonyl disulfides (5) and amino p-toluenesulfonyl sulfides (10), respectively.On the other hand, the reaction between dimorpholino sulfoxide (4) and 1 gave p-toluenesulfinylmorpholide (13).

In the presence of catalytic amounts of several amines, N,N'-thiodiphthalimide has been allowed to react with one or two equiv. of arenesulfinic acids in dichloromethane, thus giving N-(arylsulfonylthio)phthalimides or bis(arenesulfonyl) sulfides respectively in good yields.The arenesulfinate anion seems to be a better nucleophile against N,N'-thiodiphthalimide than arenesulfinic acid.The mechanism of the catalytic reaction will be discussed.

-