Dimethyl Compounds of Platinum. 3. Oxidative-Addition and Methyl-Transfer Reactions with Mercury Compounds

Novel binuclear compounds PtMe2X(HgX)(N-N) (N-N = Ph2Me2phen, X = Cl, Br, I, O2CCH3, O2CCF3; N-N = bpy, X = O2CCH3, O2CCF3) were obtained by reaction of equimolar amounts of PtMe2(N-N) and HgX2. The compounds were formed by cis oxidative addition of HgX2 to platinum. Reaction of Hg(O2CCF3)2 with PtMe2(N-N) in a ratio 1:2 resulted in the formation of trinuclear compounds Pt2Me4(O2CCF3)(HgO2CCF3)(bpy)2 and Pt2Me4(O2CCF3)2(Hg)-(Ph2Me2phen)2. Reaction with PtMe2(bpy) in a ratio 1:4 afforded a pentanuclear compound Pt4Me8(O2CCF3)-(HgO2CCF3)(bpy)4 which had a metallic appearance. The formation of MeHgO2CCF3 by a methyl-transfer reaction from PtMe2(O2CCF3)(HgO2CCF3)(N-N) to Hg(O2CCF3)2 was evidenced by 1H NMR. Reaction of MeHgO2CCF3 with PtMe2(N-N) first gave Me2Hg which reacted further (N-N = bpy) to form PtMe3(O2CCF3)(bpy). Similar reactions were observed with MeHgCl, PhHgO2CCF3, and PhHgO2CCH3. © 1978, American Chemical Society. All rights reserved.