Assembly of metal-metal bonds through small-size clusters

金属-金属键合的铂和钯的小尺寸簇作为非均相催化剂表面的最小模型越来越引起人们的兴趣；结构、性质和反应性可以通过改变合成策略和有机配体的选择来改变。报道了以双铂为前驱体，以双（二苯基膦- m -乙基）苯基膦（dpmp）为原料系统合成同源和杂三金属铂簇。[Pt_2(RNC)_6]^<2+> （RNC=芳香族异氰化物）与dpmp反应得到了顺-反-[Pt_2(dpmp)_2(RNC)_2]^<2+> （syn-1和anti-2）的异构体混合物。syn-1和反-2的不同反应性允许获得多用途的homo和hetero三核团簇聚集。前(syn-1)改变了治疗Pt ^ 0, Pt ^ <二>,Pd ^ 0, Pd ^ <二>,Rh ^我,红外^我,非盟^我Ag) ^我和铜^我物种多种Pt-Pt-M集群、线性- [Pt_2 (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Pt, Pd), asym-A-frame - [Pt_2MCl_2 (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Pt, Pd), t形——[Pt_2MCl (dpmp) _2 (RNC) _2) ^ < 2 + > (M = Ir, Rh),人字形- [Pt_2M (dpmp) _2 (RNC) _2) ^ < 3 + > (M =盟,Ag)和菱形- [Pt_2CuX (dpmp) _2] ^ < 2 + > (X = Cl, Br,我)。配合anti-2与Pt^0和Pd^0处理得到Pt-Pt-Pt和Pt-Pd-Pt a -框架簇。有趣的是，额外金属的插入位置是由两个不协调的磷化氢单位1和2的排列来调节的。还制备了二核和三核铂钼配合物，并对其进行了表征。

Metal-metal bonded small-size clusters of platinum and palladium have been of increasing interest as minimal models for the surface of heterogeneous catalysts ; structures, properties, and reactivities are able to be modified by varying the synthetic strategy and the choice of organic ligands. Systematic syntheses of homo- and heterotrimetallic platinum clusters through diplatinum precursors with bis (diphenylphosphino m ethyl) phenyl phosphine (dpmp) are reported. The reaction of [Pt_2(RNC)_6]^<2+> (RNC=aromatic isocyanide) with dpmp afforded an isomeric mixture of syn- and anti-[Pt_2(dpmp)_2(RNC)_2]^<2+> (syn-1 and anti-2). The differential reactivity of syn-1 and anti-2 allows an access to versatile aggregations of homo and hetero trinuclear clusters. The former (syn-1) was transformed by treatment with Pt^0, Pt^<II>, Pd^0, Pd^<II>, Rh^I, Ir^I, Au^I, Ag^I, and Cu^I species to a wide variety of Pt-Pt-M clusters, linear-[Pt_2(dpmp)_2(RNC)_2]^<2+> (M=Pt, Pd), asym-A-frame-[Pt_2MCl_2(dpmp)_2(RNC)_2]^<2+> (M=Pt, Pd), T-shape-[Pt_2MCl(dpmp)_2(RNC)_2]^<2+> (M=Ir, Rh), Y-shape-[Pt_2M(dpmp)_2(RNC)_2]^<3+> (M=Au, Ag), and rhombic-[Pt_2CuX(dpmp)_2]^<2+> (X=Cl, Br, I). Treatment of complex anti-2 with Pt^0 and Pd^0 species gave Pt-Pt-Pt and Pt-Pd-Pt A-frame clusters. The inserted position of an additional metal was interestingly regulated by the arrangements of two uncordinate phosphine units of 1 and 2. Di- and trinuclear plladium and molybdenum complexes with dpmp were also prepared and characterized.