METAL-COMPLEXES OF FUNCTIONALIZED SULFUR- CONTAINING LIGANDS .8. 4-PHENYL-1,2-DITHIOLANE-1-OXIDE, A STABLE, 5-MEMBERED CYCLIC THIOSULFINATE

Sensitized photooxidation of 4-phenyl-1,2-dithiolane 1 has been studie d. Reacting it with 0.5 mole equivalents of singlet oxygen, a mixture of 1, 4-phenyl-1,2-dithiolane-1-oxide 2, and 4-phenyl-1,2-dithiolane-2 -dioxide 3 is produced. Using one mole equivalent of singlet oxygen, 3 is obtained in high yields. The chemical oxidation of 1 using H2O2/HO Ac yields pure 2. With 2 a diastereoselectivity of 10:1 is observed. T he oxidative addition of 1 to L(2)Pt (eta(2)-C2H4) [L = PPh(3) (4), 1/ 2 dppe (5)] leads to the 3-phenyl-propane dithiolato complexes L(2)Pt- S-CH2-CHPh-CH2-S 6a,b. The platinum(0) compound 4 reacts with 2 to giv e the bimetallic compound [(Ph(3)P)Pt-S(O)-CH2-CHPh-CH2-mu-S](2) 7 and the monometallic species cis-(Ph(3)P)(2)Pt-S(O)-CH2-CHPh-CH2-S 8. The se complexes contain the 3-sulfido-1-(2-phenyl)-propanesulfenato ligan d. All compounds have been characterized by their spectroscopic data.