ABSTRACT
The reaction of a series of stable alpha-chlorinated oligosulfanes 2 and 3 with [Pt(eta(2)-C(2)H(4))(Ph(3)P)2] 1 have been investigated. Starting with the alpha-chlorodisulfanes 2 a,b, the platinum dichloride complex 5 and the side-on bonded thioketone platinum complexes 6 a,b were formed. Complex 1 was treated with corresponding trisulfanes 3 a,b to give 5, 6 a,b and the dithiolatocomplexes 7 a,b. We assume that the {Pt(0)(Ph(3)P)2}-complex fragment inserted along the S--S bond to form the unstable intermediate G, which decomposed to form the products described above. We could prove that the sterically crowded 1,2,4-trithiolane 8 was not involved in the reaction pathway by treatment of 1 with 8 under the same conditions; after 24 h, 8 was found to be unreacted. X-ray structure analyses were performed on complexes 6 a, 7 a and 7 b.
