Metallkomplexe mit funktionalisierten Schwefelliganden, XI [1] Herstellung von 5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxid und 1,2-Benzo-4,5,6,7-tetrathiocin-4-oxid und Reaktionen mit Platin(0)-Komplexen / Metal Complexes of Functionalized Sulfur Containing Ligands, XI [1]Synthesis of 5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxide and 1,2-Benzo-4,5,6,7-tetrathiocin-4-oxide and their Reactions with Platinum (O) Complexes

Abstract

5H-Benzo[f]-1,2,3,4-tetrathiepin-1-oxid e 5 and 1,2-Benzo-4,5.6,7-tetrathiocin-4-oxide 6 have been prepared by oxidation of the corresponding tetrasulfides 3 and 4, respectively using mCPBA in dichloromethane. The unstable bright yellow crystals of 5 were characterized by an X-ray structure determination. Lattice dimensions: a = 843,2(4), b = 468,9(2). c = 2409.5(14) pm. b = 95,19(4)°; space group P2,/n, Z = 4. The platinum(O) compounds L2Pt(η2-C2H4) [7a: L = 1/2 Fe(η5-C5H4PPh2)2, 7b: L = (-)-DIOP] react with the tetrasulfide oxides 5 and 6 to give products of an oxidative addition of sulfur, the sulfido bridged diplatinum complexes [L2Pt(μ-S)]2 [8a: L = 1/2 Fe(η-C5H4PPh2)2, 8b: L = (-) - DIOP] . When the reaction is carried out with 6 and 7b, the thiosulfinate 9 is identified together with 8b. The former is a co-product of the desulfurization followed by a ring-contraction of 6.