Metallkomplexe mit funktionalisierten Schwefelliganden, XI [1] Herstellung von 5H-Benzo[f]-l,2,3,4-tetrathiepin-l-oxid und 1.2-Benzo-4,5,6,7-tetrathiocin-4-oxid und Reaktionen mit Platin(0)-Komplexen

Tetrathiepin, Pentathiocin. Tetrathiepin-S-oxide, Tetrathiocin-S-oxide, Platinum C om plexes 5H -B en zo[f]-l,2 ,3 ,4-tetrath iep in-l-oxide 5 and l,2-B enzo-4,5.6,7-tetrath iocin-4-oxide 6 have been prepared by oxidation of the corresponding tetrasulfides 3 and 4, respectively using w C P B A in dichlorom ethane. The unstable bright yellow crystals o f 5 were characterized by an X-ray structure determ ination. Lattice dim ensions: a = 843,2(4), b = 468,9(2). c = 2409.5(14) pm. b = 95,19(4)°; space group P 2,/n , Z = 4. The platinum(O) com ­ pounds L2Pt(>/2-C2H 4) [7a: L = 1/2 Fe(>/5-C5H 4PPh2)2, 7b: L = ( ) -D I O P ] react with the tetrasulfide oxides 5 and 6 to give products o f an oxidative addition o f sulfur, the sulfido bridged diplatinum com plexes [L2Pt(/<-S)]2 [8a: L = 1/2 Fe(;/'1-C sH 4PPh2)2, 8b: L = ( ) -D I O P ] . W hen the reaction is carried out with 6 and 7b, the thiosulfinate 9 is identified together with 8b. The former is a co-product o f the desulfurization fo llow ed by a ring-contraction o f 6.