Coordination Chemistry of Dithiazolyl Radicals.

Reaction of benzo-1,2,3-dithiazolyl, 1 , with Pt(PPh 3 ) 4 has been shown to produce the aminothiolate complex (amt)Pt(PPh 3 ) 2 [amt = HNC 6 H 4 S], via oxidative addition of 1 to Pt(PPh 3 ) 2 followed by S-abstraction by PPh 3 . 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(PR 3 ) 2 induces electron transfer from Pt(PR 3 ) 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. [ABSTRACT FROM AUTHOR]