Reactivity of [M(C∧P)(S2CNMe2)] [M = Pt, Pd; C∧P = CH2−C6H4−P(o-tolyl)2-κC,P] toward Mercury(II) Carboxylates. X-ray Molecular Structures of [Pt(C∧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{CH 2 −C 6 H 4 −P( o -tolyl) 2 -κ C, P }(S 2 CNMe 2 )] ( A ) with an equimolar amount of Hg(O 2 CR) 2 (R = CH 3, CF 3 ) gives the binuclear compounds OC-6 - 23 [Pt(C∧P)(S 2 CNMe 2 )(O 2 CR)Hg(O 2 CR)] [R = CH 3 ( 1 ), CF 3 ( 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{CH 2 −C 6 H 4 −P( o -tolyl) 2 -κ C, P }(S 2 CNMe 2 )] ( B ) with Hg(O 2 CR) 2 (R = CH 3, CF 3 ) in a 1:1 molar ratio leads to the corresponding binuclear complexes [Pd(S 2 CNMe 2 ){μ-P( o -tolyl) 2 −C 6 H 4 −CH 2 −}(μ-O 2 CR)Hg(O 2 CR)] [R = CH 3 ( 3 ), CF 3 ( 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.