Behavior of Neutral Phosphido Derivatives of Platinum and Palladium toward Silver Centers

The reaction of the neutral binuclear complexes [(R(F))(2)Pt(mu-PPh(2))(2)M(Phen)1 (phen = 1,10-phenanthroline, R(F) = C(6)F(5); M = Pt, 1; M = Pd, 2) with AgClO(4) or [Ag(OClO(3))(PPh(3))] affords the trinuclear complexes [AgPt(2)(mu-PPh(2))(2)(R(F))(2)(Phen)(OClO(3))] (7a) or [AgPtM(mu-PPh(2))(2)(RF)(2)(Phen)(PPh(3))] [ClO(4)] (M = Pt, 8; M = Pd, 9), which display an "open-book" type structure and two (7a) or one (8,9) Pt Ag bonds. The neutral diphosphine complexes [(R(F))(2)Pr(mu-PPh(2))(2)m(P P)] (P P = 1,2-bis(diphenylphosphino)methane, dppm, M = Pt, 3; M = Pd, 4; P P = 1,2-bis(diphenylphosphino)ethane, dppe, M = Pt, 5; M = Pd, 6) react with AgClO(4) or [Ag(OClO(3))(PPh(3))], and the nature of the resulting complexes is dependent on both M and the diphosphine. The dppm Pt Pt complex 3 reacts with [Ag(OClO(3))(PPh(3))], affording a silver adduct 10 in which the Ag atom interacts with the Pt atoms, while the dppm Pt Pd complex 4 reacts with [Ag(OClO(3))(PPh(3))], forming a 1:1 mixture of [AgPdPt(mu-PPh(2))(2)(RF)(2)(OClO(3))(dppm)] (11), in which the silver atom is connected to the Pt-Pd moiety through Pd (mu-PPh(2)) Ag and Ag-P(k'-dppm) interactions, and [AgPdPt(mu-PPh(2))(2) (R(F))(2)(OClO(3))(PPh(3))(2)] [ClO(4)] (12). The reaction of complex 4 with AgClO(4) gives the trinuclear derivative 11 as the only product. Complex 11 shows a dynamic process in solution in which the silver atom interacts alternatively with both Pd-mu PPh(2) bonds. When P-P is dppe, both complexes 5 and 6 react with AgClO(4) or [Ag(OClO(3))(PPh(3))], forming the saturated complexes (M = Pt, 13; Pd, 14), which are the result of an oxidation followed by a PPh(2)/C(6)F(5) reductive coupling. Finally, the oxidation of trinuclear derivatives [(R(F))(2)Pt(II)(mu-PPh(2))(2)Pt(II)(mu-4PPh(2))(2)Pt(II)L(2)] (L(2) = phen, 15; L = PPh(3), 16) by AgClO(4) results in the formation of the unsaturated 46 VEC complexes [(R(F))(2)Pt(III)(mu-PPh(2))(2)Pt(III)(mu-PPh(2))(2)Pt(II)L(2)][ClO(4)](2) (17 and 18, respectively) which display Pt(III)-Pt(III) bonds.