Stereoselective oxidative addition of methyl iodide to chiral cyclometallated platinum(II) compounds derived from (R)-(+)-1-(1-naphthylethylamine). Crystal structure of [PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3]

The reaction of 3-(R)-(C10H7)CHMeNCHC4H3S (2a) with [Pt2Me4(mu -SMe2)(2)] i n acetone gave the new chiral cyclometallated platinum(II) compound [PtMe{3 -(R)-(C10H7)CHMeNCHC4H2S}SMe2] (3a). Addition of PPh3 produced compound [Pt Me{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3] (4a) which was characterized by X-ray di ffraction methods. While oxidative addition of methyl iodide to 3a gave two pairs of diastereomers, the analogous reaction for 4a produced only one di astereomer of the platinum(IV) compound [PtMe2I{3-(R)-(C10H7)CHMeNCHC4H2S}P Ph3] (7a). Subsequent isomerization of the resulting platinum(IV) compound gave a new pair of diastereomers in relative amounts 90 and 10%. Analogous proportions of final diastereomers were obtained for the oxidative addition of methyl iodide to the new chiral compounds [PtMe{3-(R)-(C10H7)CHMeNCHAr} PPh3] (Ar = C6H4 (4b), 2-FC6H3 (4c), 2-CF3C6H3 (4d)). The reaction of [Pt2M e4(mu -SMe2)(2)] with imines (R)-(C10H7)CHMeNCH(2-BrC6H4) (2e) and (R)-(C10 H7)CHMeNCH(2,6-Cl2C6H3) (2f) produced intramolecular oxidative addition to yield platinum(IV) compounds with some degree of stereoselectivity. (C) 200 1 Elsevier Science BN. All rights reserved.