Reactivity of [M(C∧P)(S2CNMe2)] [M = Pt, Pd; Cr∧P = CH2-C6H4-P(o-tolyl)2-κC,P] toward mercury(II) carboxylates.: X-ray molecular structures of [Pt(Cr∧P)-(S2CNMe2)(O2CCF3)Hg(O2CCF3)] and [Pd(S2CNMe2)-{μ-P(o-tolyl)2-C6H4-CH2-}(μ-O2CCH3)Hg(O2CCH3)]

The reaction of the complex [Pt{CH2-C6H4-P(o-tolyl)(2-kappa)C,P}(S2CNMe2)] (A) with an equimolar amount of Hg(O2CR)(2) (R = CH3, CF3) gives the binuclear compounds OC-6-23 [Pt(C boolean AND 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-kappa)C,P}(S2CNMe2)] (B) with Hg(O2CR)2 (R = CH3, CH3) in a 1:1 molar ratio leads to the corresponding binuclear complexes [Pd(S2CNMe2){mu-P(o-tolyl)(2)-C6H4-CH2-}(mu-O2CR)Hg(O2CR)] [R = CH3 (3), CF3 (4)] with the bidentate C boolean AND 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.