3,3,5,5-Tetraphenyl-1,2,4-trithiolane (1) reacts with twofold excess of (Ph3P)2Pt(η2-C2H4) (4) to give a 1:1 mixture of the complexes (Ph3P)2
(6a) and (Ph3P)2Pt(η2-Ph2C=S) (7a). Treatment of 3,3,6,6-tetraphenyl-1,2,4,5-tetrathiane (2) with a fourfold excess of 4 yields [Pt2(PPh3)4(μ-S)2] (8) and the platinum(O) compound 7a. The reaction of the 1,2,3,5,6- pentathiepane 3 with a fourfold excess of 4 affords a 1:1:1 mixture of 8, the platinum(O) complex 7b and the bis-thiolato platinum(II) complex 6b. The thioketone complexes 7a-c were formed in smooth reactions of 4 with the thioketones 5a-c. The molecular structure of (Ph3P)2Pt(η2-Ph2C=S) (7a) has been established by single-crystal X-ray analysis.