Reactivity of [M(C∧P)(S<sub>2</sub>CNMe<sub>2</sub>)] [M = Pt, Pd; C∧P = CH<sub>2</sub>−C<sub>6</sub>H<sub>4</sub>−P(<i>o</i>-tolyl)<sub>2</sub>-κ<i>C</i>,<i>P</i>] toward Mercury(II) Carboxylates. X-ray Molecular Structures of [Pt(C∧P)(S<sub>2</sub>CNMe<sub>2</sub>)(O<sub>2</sub>CCF<sub>3</sub>)Hg(O<sub>2</sub>CCF<sub>3</sub>)] and [Pd(S<sub>2</sub>CNMe<sub>2</sub>){μ-P(<i>o</i>-tolyl)<sub>2</sub>−C<sub>6</sub>H<sub>4</sub>−CH<sub>2</sub>−}(μ-O<sub>2</sub>CCH<sub>3</sub>)Hg(O<sub>2</sub>CCH<sub>3</sub>)]
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The reaction of the complex [Pt{CH2−C6H4−P(o-tolyl)2-κC,P}(S2CNMe2)] (A) with an equimolar amount of Hg(O2CR)2 (R = CH3, CF3) gives the binuclear compounds OC-6-23 [Pt(C∧P)(S2CNMe2)(O2CR)Hg(O2CR)] [R = CH3 (1), CF3 (2)] containing a Pt−Hg covalent bond. These compounds result from the cis oxidative addition of the mercury(II) carboxylate to complex A. A concerted mechanism involving a platinum to mercury donor bond intermediate is proposed. The reaction of the complex [Pd{CH2−C6H4−P(o-tolyl)2-κC,P}(S2CNMe2)] (B) with Hg(O2CR)2 (R = CH3, CF3) in a 1:1 molar ratio leads to the corresponding binuclear complexes [Pd(S2CNMe2){μ-P(o-tolyl)2−C6H4−CH2−}(μ-O2CR)Hg(O2CR)] [R = CH3 (3), CF3 (4)] with the bidentate C∧P ligand acting as an unusual bridging group. Compounds 3 and 4 come from a transmetalation process without the complete transference of the ligand from Pd to Hg.
