Reactions of {[Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd](&mgr;-SC(6)F(5))}(4).2O(C(2)H(5))(2). Crystal Structures of the Complexes [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))].1.4CH(2)Cl(2) and [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(PPh(3))]SO(3)CF(3).2CH(2)Cl(2) and ab Initio MO Calculations on the Model Systems [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))(&mgr;-SH)Pd(PH(3))](+) and [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))Pd(PH(3))](2+).

{[Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd](&mgr;-SC(6)F(5))}(4) reacts 1:4 with neutral ligands L to give [LPd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))] or 1:8 to form [LPd(&mgr;-SC(6)F(5))(&mgr;-dppm)PdL](+) (dppm = bis(diphenylphosphino)methane). These binuclear complexes retain the palladium-palladium bond and the two dissimilar bridging ligands, as demonstrated by the X-ray structural determinations carried out on [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))].1.

Synthesis of Heteronuclear Pt-Tl Complexes with Donor-Acceptor Bonds. X-ray Structures of cis-[Tl(&mgr;(2)-OOCCH(3))Pt(PPh(3))(C(6)F(5))(2)] and (NBu(4))(2)[{Pt(C(6)F(5))(3)}(2){(&mgr;(2)-O,&mgr;(3)-O'CCH(3))Tl}(2)].

Reactions of the anionic platinum complexes (NBu(4))[Pt(PPh(3))(C(6)F(5))(2)(OCOCH(3))] (1) and (NBu(4))(2)[Pt(C(6)F(5))(3)(S)] (S = methanol or acetone) with Tl(I) salts afford the heterometallic neutral cis-[(C(6)F(5))(2)(PPh(3))Pt(&mgr;(2)-OOCCH(3))Tl] (2) and the dimeric dianionic (NBu(4))(2)[{(C(6)F(5))(3)Pt}(2){(&mgr;(2)-O,&mgr;(3)-O'CCH(3))Tl}(2)] (3). Both complexes display Pt-Tl bonds with bond lengths of 2.994(1) Å and 2.