Dimethyl Compounds of Platinum(II). 2. Reactions Involving Carbon-, Silicon-, and Germanium-Halogen Bonds

Abstract

Reactions of [Formulla Omitted] bipyridine, 2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline) afforded the new compounds [PtMe2X(GeRnX3_n)(N-N)]. The compounds were stable to H2O, alcohol (except for n = 3), pyridine, and PPh3. Compounds with formula [PtMe2X(GeR3)(bpy)] (R = Me, Ph; X = Cl) were not stable in solution and decomposed to PtMe2Cl(CH2Cl)(bpy). Exchange reactions of [PtMe2Cl(MRnCl3-n)(bpy)] with M'RmCl4_m (M, M' = Ge, Sn, Pb) were studied. Reactions with [GeR3Br] resulted in bromine exchange. In the presence of moisture SiRnCl4_n (R = Ph, Me; n = 0, 1,2) reacted with PtMe2(bpy) in CH2C12 to give PtMeCl(bpy). Reactions of CRnC14_n gave the following results (R = Ph, Me; n = 0, 1, 2, 3): Trans oxidative addition occurred with CC14 and CPhCl3. With CPh2Cl2 and CPh3Cl the compound PtMe2Cl2(bpy) was obtained. With CMeCl3 trans addition and further reaction to the vinyl compound [PtMe2Cl(CH2CCl)(bpy)] occurred. No reaction was observed with CMe3Cl. Reactions of CH.C14_. (n = 0, 2, 3) proceeded via trans oxidative addition to [PtMe2Cl-(CHnCl3_n)(bpy)], except in the case of CH2C12 when also cis addition was observed. The rate of the conversion cis → trans was enhanced by added SiPh3Cl. © 1978, American Chemical Society. All rights reserved.