Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu<sub>4</sub>]<sub>2</sub>[{Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(<i>μ</i>-SH)}<sub>2</sub>], [Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(PPh<sub>3</sub>){S(H)AgPPh<sub>3</sub>}], and [Pt(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>(PPh<sub>3</sub>){S(AuPPh<sub>3</sub>)<sub>2</sub>}]
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The reactions of the hydroxo complexes [M2R4(μ-OH)2]2- (M = Pd, R = C6F5, C6Cl5; M = Pt, R = C6F5), [{PdR(PPh3)(μ-OH)}2] (R = C6F5, C6Cl5), and [{Pt(C6F5)2}2(μ-OH)(μ-pz)]2- (pz = pyrazolate) with H2S yield the corresponding hydrosulfido complexes [M2(C6F5)4(μ-SH)2]2-, [{PdR(PPh3)(μ-SH)}2], and [{Pt(C6F5)2}2(μ-SH)(μ-pz)]2-, respectively. The monomeric hydrosulfido complexes [M(C6F5)2(SH)(PPh3)]- (M = Pd, Pt) have been prepared by reactions of the corresponding binuclear hydrosulfido complexes [M2(C6F5)4(μ-SH)2]2- with PPh3 in the molar ratio 1:2, and they can be used as metalloligands toward Ag(PPh3)+ to form the heterodinuclear complex [(C6F5)2(PPh3){S(H)AgPPh3}], and toward Au(PPh3)+ yielding the heterotrinuclear complexes [M(C6F5)2(PPh3){S(AuPPh3)2}]. The crystal structures of [NBu4]2[{Pt(C6F5)2(μ-SH)}2], [Pt(C6F5)2(PPh3){S(H)AgPPh3}], and [Pt(C6F5)2(PPh3){S(AuPPh3)2}] have been established by X-ray diffraction and show no short metal−metal interactions between the metallic centers.
