Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea, Universidad de Zaragoza -C.S.I.C., E-50009 Zaragoza, Spain.
Inorg Chem. 2011 Nov 7;50(21):10798-809. doi: 10.1021/ic201354s. Epub 2011 Sep 26.
The reaction of the neutral binuclear complexes [(R(F))(2)Pt(μ-PPh(2))(2)M(phen)] (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)(μ-PPh(2))(2)(R(F))(2)(phen)(OClO(3))] (7a) or [AgPtM(μ-PPh(2))(2)(R(F))(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)Pt(μ-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(μ-PPh(2))(2)(R(F))(2)(OClO(3))(dppm)] (11), in which the silver atom is connected to the Pt-Pd moiety through Pd-(μ-PPh(2))-Ag and Ag-P(k(1)-dppm) interactions, and [AgPdPt(μ-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-μPPh(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 [(PPh(2)C(6)F(5))(R(F))Pt(μ-PPh(2))(μ-OH)M(dppe)][ClO(4)] (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)(μ-PPh(2))(2)Pt(II)(μ-PPh(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)(μ-PPh(2))(2)Pt(III)(μ-PPh(2))(2)Pt(II)L(2)]ClO(4) (17 and 18, respectively) which display Pt(III)-Pt(III) bonds.
中性双核配合物[(R(F))(2)Pt(μ-PPh(2))(2)M(phen)]（phen=1,10-菲咯啉，R(F)=C(6)F(5)；M=Pt，1；M=Pd，2）与 AgClO(4)或[Ag(OClO(3))(PPh(3))]反应得到三核配合物[AgPt(2)(μ-PPh(2))(2)(R(F))(2)(phen)(OClO(3))]（7a）或[AgPtM(μ-PPh(2))(2)(R(F))(2)(phen)(PPh(3))][ClO(4)]（M=Pt，8；M=Pd，9），它们呈现出“开页式”结构和两个（7a）或一个（8、9）Pt-Ag 键。中性双膦配合物[(R(F))(2)Pt(μ-PPh(2))(2)M(P-P)]（P-P=1,2-双（二苯基膦基）甲烷，dppm，M=Pt，3；M=Pd，4；P-P=1,2-双（二苯基膦基）乙烷，dppe，M=Pt，5；M=Pd，6）与 AgClO(4)或[Ag(OClO(3))(PPh(3))]反应，所得配合物的性质取决于 M 和双膦配体。dppm Pt-Pt 配合物 3 与[Ag(OClO(3))(PPh(3))]反应，生成银加合物 10，其中 Ag 原子与 Pt 原子相互作用，而 dppm Pt-Pd 配合物 4 与[Ag(OClO(3))(PPh(3))]反应，形成 1:1 的混合物[AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(dppm)]（11），其中 Ag 原子通过 Pd-(μ-PPh(2))-Ag 和 Ag-P(k(1)-dppm)相互作用与 Pt-Pd 部分相连，以及[AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(PPh(3))(2)][ClO(4)]（12）。配合物 4 与 AgClO(4)反应仅得到三核衍生物 11 作为唯一产物。配合物 11 在溶液中表现出动态过程，其中 Ag 原子交替与两个 Pd-μPPh(2)键相互作用。当 P-P 为 dppe 时，配合物 5 和 6 都与 AgClO(4)或[Ag(OClO(3))(PPh(3))]反应，形成饱和配合物[(PPh(2)C(6)F(5))(R(F))Pt(μ-PPh(2))(μ-OH)M(dppe)][ClO(4)]（M=Pt，13；Pd，14），这是氧化后紧接着发生 PPh(2)/C(6)F(5)还原偶联的结果。最后，三核衍生物[(R(F))(2)Pt(II)(μ-PPh(2))(2)Pt(II)(μ-PPh(2))(2)Pt(II)L(2)]（L(2)=phen，15；L=PPh(3)，16）被 AgClO(4)氧化生成不饱和 46 VEC 配合物[(R(F))(2)Pt(III)(μ-PPh(2))(2)Pt(III)(μ-PPh(2))(2)Pt(II)L(2)]ClO(4)（17 和 18，分别），其中含有 Pt(III)-Pt(III)键。
