COORDINATION CHEMISTRY OF DITHIAZOLYL RADICALS

Reaction of benzo-1,2,3-dithiazolyl, 1, with Pt(PPh₃)₄ has been shown to produce the aminothiolate complex (amt)Pt(PPh₃)₂ amt = HNC₆H₄S], via oxidative addition of 1 to Pt(PPh₃)₂ followed by S-abstraction by PPh₃. Semi-empirical calculations (AM1 and EHT) have been used to probe the oxidative addition step of this reaction. These studies clearly reveal that close approach of 1 to Pt(PR₃)₂ induces electron transfer from Pt(PR₃)₂ to 1 with concomitant ring opening at the S─N bond and coordination to the metal centre. The SOMO of this complex retains the π* character of the dithiazolyl ring.