Inorganic Chemistry, Vol.40, No.21, 5354-5360, 2001
Synthesis and reactivity of bridging and terminal hydrosulfido palladium and platinum complexes. Crystal structures of [NBu4](2)[{Pt(C6F5)(2)(mu-SH}(2)], [Pt(C6F5)(2)(PPh3){S(H)AgPPh3}], and [Pt(C6F5)(2)(PPh3){S(AuPPh3)(2)}]
The reactions of the hydroxo complexes [M2R4(mu -OH)(2)](2-) (M = Pd, R = C6F5, C6Cl5; M = Pt, R = C6F5), [{PdR(PPh3)(mu -OH)}(2)] (R = C6F5, C6Cl5), and [{Pt(C6F5)(2)}(2)(mu -OH)(mu -pz)](2-) (pz = pyrazolate) with H2S yield the corresponding hydrosulfido complexes [M-2(C6F5)(4)(mu -SH)(2)](2-), [{PdR(PPh3)(mu -SH)}(2)], and [{Pt(C6F5)(2)}(2)(mu -SH)(mu -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(A-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)(mu -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.