Metallkomplexe mit funktionalisierten Schwefelliganden, VIII [1]. 4-Phenyl-1,2-dithiolan-1-oxid, ein stabiles, fünfgliedriges cyclisches Thiosulfinat / Metal Complexes of Funetionalized Sulfur Containing Ligands, VIII [1]. 4-Phenyl-1,2-dithiolane-1-oxide, a Stable, Five-Membered Cyclic Thiosulfinate

Abstract

Sensitized photooxidation of 4-phenyl-1,2-dithiolane 1 has been studied. Reacting it with 0.5 mole equivalents o f 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/HOAc yields pure 2. With 2 a diastereoselectivity of 10:1 is observed. The oxidative addition of 1 to L2Pt(η2-C2H4)[L=PPh3 (4), 1/2 dppe (5)] leads to the 3-phenyl-propane dithiolato complexes 6a,b. The platinum(O) com pound 4 reacts with 2 to give the bimetallic compound 7 and the monometallic species . These complexes contain the 3-sulfido-l-(2-phenyl)-propanesulfenato ligand. All com pounds have been characterized by their spec­ troscopic data.

Correlation between the Molecular Structure and Photoresponse in Aliphatic Self-Assembled Monolayers with Azobenzene Tailgroups

“…−4680 ppm. These NMR spectroscopic values are in accord with data obtained for closely related six-membered platinacycles. , The crystal structure of the amide derivative 3 was determined by single-crystal X-ray diffraction. The respective molecular structure is shown in Figure .…”

Oxidative addition of asparagusic acid based disulfides to Pt0

“…The corresponding 195 Pt NMR signal appears as a doublet with a chemical shift value in the range between À4700 and À4612 ppm. These NMR spectroscopic values are in accord with data obtained for closely related six-membered platinacycles [13,18]. The crystal structures of 7 Bond parameters compare well with those of closely related compounds [19].…”

Oxidation induced by the antioxidant glutathione (GSH)

“…15 The formation of peroxo species is known to occur during the oxidation of thiolato complexes and sulfides, as well as disulfides, with singlet oxygen. [16][17][18][19][20][21] Transfer of oxygen atoms from an initial peroxo species formed by reaction of a thioether with singlet oxygen to another thioether has been observed in well selected thioether couples. 21 If this pathway prevails, then addition of hydrogen peroxide should lead to the preferential oxidation of the thiolato complex 1a instead of GSH.…”