Metallkomplexe rnit funktionalisierten Schwefel-Liganden, Ill['] Reaktionen von (Ph3P)2Pt(q2-C2H4) mit acyclischen und cyclischen Thiosulfinaten: Platin(I1)-thiolato-Komplexe mit Sulfenato-Liganden. Kristallstrukturanalyse von (4-Sulfido-l-b,utansulfenato-S.S')bis(triphenylphosphan)platin(II) (Ph3P),Pt -S(0) -[CH214 -S* Metal Complexes of Functionalized Sulfur-Containing Ligands, IIItll. -Reactions of (Ph3P)2Pt(qZ-C2H4) with Acyclic and Cyclic Thiosulfinates: Platinum(I1)-thiolato Complexes with Sulfenato Ligands. Crystal Structure Determination of (4-Sulfido-l-butanesulfenato-S,S')bis(triphenylphosphane)platinum(II) (Ph,P),P\ -S(0) -[CH2l4 -9 *
The platinum(O) compound (Ph3P)2Pt(η2H4) (1) reacts with N-(alkyl- and arylsulfinyl) phthalimides R—S(O)-Nphth [R = C3H7 (2a), C4H9 (2b), C12H25 (2c), CH2Ph (2d), Ph (2e) p-CH3C6H4 (2f)] to give the trans-configurated sulfenato complexes (Ph3P)2Pt[S(O)—R](Nphth) (3a—f). The compounds 3a—f have been characterized by IR, 1H, 13C and 31P NMR spectroscopy, 3d—f additionally by their FAB mass spectra. The oxidation of cis-(Ph3P)2Pt(SC4H9)(Nphth) (5) with m-chloroperbenzoic acid leads to a mixture of compounds containing cis-(Ph3P)2Pt[S(O)C4H9](Nphth) (6) as a main product.
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.
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