OXIDATIVE ADDITION OF UNSATURATED CYCLIC 5-MEMBERED DISULFIDES TO RHCL(PPH3)3 AND PT(PPH3)4

The reaction of RhCl(PPh3)3 with the cyclic disulfides hexachloronaphthalene-l,8-disulfide (S2 C10Cl6), 4-phenyl-l,2-dithiolium chloride ([HC(S)C(Ph)C(S)H]Cl) and 3,5-bis(dimethylamino-1,2,4-dithiazolium chloride ([Me2NC(S)NC(S)NMe2]Cl) results, via oxidative addition of the SS bond, in the complexes RhCl(S2C10Cl6)(PPh3)2 , RhCl2[HC(S)C(Ph)C(S)]H](IPPh3)2 and RhCl2[Me2NC(S)NC(S)NMe2][PPh3) 2, respectively. Upon reaction of Pt(PPh3) 4 with [HC[S]C(Ph)C(S)H] Cl cis-PtCl2(PPh3)2 is formed and no (β-dithioketonato)Pt(II) complex. The reaction of Pt(PPh3)4 with [Me2NC(S)NC(S)NMe2] Cl is solvent dependent: in chloroform Pt {[Me2NC(S)NC(S)NMe2](PPh3)2} Cl and in benzene Pt[Me2NC(S)NC(S)NMe2]Cl(PPh3) is formed. © 1979.