Diastereoselective oxidative addition of cyclic thiosulfinates to platinum(0) compounds: chiral platinum(II) complexes with sulfenato ligands Crystal structures of S(O)–CH2–CH(OAc)–CH(OAc)–CH2–S and dppePt[S(O)–(CH2)4–S]: Part 16. Metal complexes of funct

The oxidative addition reactions of the racemic thiosulfinates (O) (1) and (O) (4) with dppePt(η2-C2H4) (6) led to the 1-sulfenato-4-thiolato platinum(II) complexes dppePt[S(O)–(CH2)4–S] (8) and dppePt[S(O)–CH2–(C6H4)–CH2–S] (9); the crystal structure of complex 8 was determined. The oxidative addition of the racemic thiosulfinate (O) [(R*SO, R*, R*)-2] to (Ph3P)2Pt(η2-C2H4) (5) gave two diastereoisomers of compound (Ph3P)2Pt[S(O)–CH2–CH(OAc)–CH(OAc)–CH2–S] (10) in a ratio 1:1. The thiosulfinates [(R*SO, R*,R*)-2] and [(R*SO,R*,S*)-3] reacted with [(R, R-diop)]Pt(η2-C2H4) (7) to yield four diastereoisomers each of the complexes [(R,R-diop)]Pt[S(O)–CH2–CH(OAc)–CH(OAc)–CH2–S] (11) and 12 in a ratio 100:100:1:1 and 10:10:1:1, respectively. [(R*SO, R*, S*)-3] was characterized structurally. Treatment of the mixture of diastereoisomers of complex 11 with two equivalents of dppe gave only one diastereoisomer of complex dppePt[S(O)–CH2–CH(OAc)–CH(OAc)–CH2–S] (13).