Diverse reactions of S–S function under metal-mediated and metal-free thermolysis conditions

Parallel comparative studies on reactivities of S–S function in 2-ppds (2-ppds = bis(4-(pyridin-2-yl)pyrimidin-2-yl)disulfane) have been carried out under the same thermolysis conditions. In the presence of FeCl2, thermolysis reaction of 2-ppds in the MeOH/CH2Cl2 mixture results in a mononuclear compound [FeCl2(2-pps)] with newly generated organic ligand 2-pps (2-pps = bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane). In the absence of FeCl2, the result of solvolysis depends upon the conditions. Thus, in pure MeOH, 2-ppds partially converts into a mixture of S-(4-pyridin-2-yl)pyrimidin-2-yl (4-pyridin-2-yl)pyrimidine-2-sulfonothioate (2-ppst) and 2-pps, while in a MeOH/CH2Cl2 mixture, 2-(chloromethylthio)-4-(pyridin-2-yl)pyrimidine (2-ppct) is the main product.