Reactivity of [M(C∧P)(S2C-R)] (M = Pd, Pt; C∧P = CH2-C6H4-P(o-tolyl)2-κC,P; R = NMe2, OEt) toward HgX2 (X = Br, I). X-ray Crystal Structures of [Pt{CH2-C6H4P(o-tolyl)2-κC,P}(S2CNMe2)HgI(μ-I)]2 and [PdBr(S2COEt){μ-P(o-tolyl)2-C6H4-CH2-}HgBr]·0.5HgBr2·C2H4Cl2

The reaction of the complexes [Pt(C∧P)(S 2 C-R)] (C∧P = CH 2 -C 6 H 4 -P( o -tolyl) 2 -κ C, P, R = NMe 2, OEt) with an equimolar amount of HgX 2 (X = Cl, Br) gives the tetranuclear derivatives [Pt(C∧P)(S 2 C-R)HgX(μ-X)] 2 [R = NMe 2, X = Br ( 3 ), I ( 4 ); R = OEt, X = Br ( 5 ), I ( 6 )] containing Pt→Hg donor−acceptor bonds. The reaction of [Pd(C∧P)(S 2 CNMe 2 )] with HgI 2 affords the complex [Pd(C∧P)(S 2 CNMe 2 )HgI(μ-I)] 2 ( 9 ) similar to the complexes 3 − 6; by contrast the reaction of [Pd(C∧P)(S 2 C-R)] (R = NMe 2, OEt 2 ) with HgBr 2 leads to the corresponding dinuclear complexes [PdBr(S 2 C-R)(μ-C∧P)HgBr] [R = NMe 2 ( 10 ), OEt ( 11 )] with the didentate C∧P cyclometalating ligand, −CH 2 -C 6 H 4 -P( o -tolyl) 2 - C, P (resulting from the C−H activation of the P( o -tolyl) 3 ) acting in an unprecedented bridging mode. Compound 4 (C 24 H 26 HgI 2 NPPtS 2 ) crystallizes in the triclinic system, space group P 1̄: a = 9.5755(11) Å, b = 11.1754(12) Å, c = 14.504(2) Å, α = 84.826(5)°, β = 81.611(7)°, γ = 68.606(9)°, V = 1428.5(3) Å 3, and Z = 1. Compound 11 ·0.5 HgBr 2 ·C 2 H 4 Cl 2 (C 24 H 25 Br 2 HgOPPdS 2 ·0.5 HgBr 2 ·C 2 H 4 Cl 2 ) crystallizes in the monoclinic system, space group P 2 1 / c: a = 15.571(2) Å, b = 10.7425(10) Å, c = 19.655(2) Å, β = 94.741(12)°, V = 3276.5(5) Å 3, and Z = 4.