Study on Platinum( II ) Induced Formation of Dithiiranes

The reaction of a series of stable α‐chlorinated oligosulfanes 2 and 3 with [Pt(η 2 ‐C 2 H 4 )(Ph 3 P) 2 ] 1 have been investigated. Starting with the α‐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 SS 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 .