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Assembly of metal-metal bonds through small-size clusters

通过小尺寸簇组装金属-金属键

基本信息

批准号：
08640725
负责人：
TANASE Tomoaki
金额：
$ 1.41万
依托单位：
Nara Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640725/
关键词：
metal cluster metal-metal bond tridentate phosphine platinum complex trinuclear complex heterometal cluster catalyst model transition metal 3座ホスフィン配位子 3核錯体

项目摘要

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.

金属-金属键合的铂和钯的小尺寸簇合物作为非均相催化剂表面的最小模型已经引起越来越多的兴趣;结构、性质和反应性能够通过改变合成策略和有机配体的选择来修改。以双（二苯基膦甲基）苯基膦（dpmp）为前驱体，系统地合成了均三金属铂簇和异三金属铂簇。[Pt_2（RNC）_6]^<2+>（RNC=芳香异腈）与dpmp反应，得到顺式和反式[Pt_2（dpmp）_2（RNC）_2]^<2+>（顺式-1和反式-2）的异构体混合物。syn-1和抗-2的差异反应性允许获得同源和异源三核簇的多功能聚集体。前者（syn-1）经Pt^0、Pt^<II>、Pd^0、Pd^<II>、Rh^I、Ir^I、Au^I、Ag^I和Cu^I处理后，转化为多种Pt-Pt-M簇合物，即线性的-[Pt_2（dpmp）_2（RNC）_2]^<2+>（M=Pt，Pd），非对称-A-框架-[Pt_2MCl_2（dpmp）_2（RNC）_2]^<2+>（M=Pt，Pd）、T型-[Pt_2MCl（dpmp）_2（RNC）_2]^<2+>（M=Ir，Rh）、Y型-[Pt_2M（dpmp）_2（RNC）_2]^<3+>（M=Au，Ag）和菱形-[Pt_2CuX（dpmp）_2]^<2+>（X=Cl，Br，I）。用Pt^0和Pd^0处理反-2络合物，得到Pt-Pt-Pt和Pt-Pd-Pt A-框架簇合物。有趣的是，另外一种金属的插入位置由两个不协调的膦单元1和2的排列来调节。还制备了双核和三核钯、钼与dpmp的配合物并进行了表征。