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小簇作为异质催化剂表面的最小模型引起了人们的兴趣。结构，性质和反应能力可以通过改变合成策略和有机配体的选择来修改。据报道，通过BIS（二苯基磷酸M乙基）苯基磷蛋白（DPMP），通过外交前体前体（DPMP）的同型和杂质铂簇的系统合成。 [PT_2（RNC）_6]^<2+>（RNC =芳香族异氰化物）与DPMP的反应提供了同步和抗[pt_2（dpmp）_2（rnc）_2] _2] _2]^<2+>（syn-1和antim-1和anti-1和anti-1和anti-1和anti-1和抗2）的异构混合物。 SYN-1和抗2的差异反应性允许访问HOMO和Hetero三核簇的多功能聚集。前者（SYN-1）通过Pt^0，pt^<ii>，pd^0，pd^<ii>，rh^i，ir^i，au^i，ag^i，ag^i和cu^i的种类转化为多种PT-PT-M簇，线性 - 线性 - [pt_2（dpmp）_2（dpmp）_2（dpmp）_2（ppmp）_2（rnc）_2（rnc）_2 _2] asym-a-frame- [pt_2mcl_2（dpmp）_2（rnc）_2] _2]^<2+>（m = pt，pt，pd），t-shape- [pt_2mcl（dpmp）_2（rnc）_2（rnc）_2] _2] _2] y-shape- [pt_2m（dpmp）_2（rnc）_2]^<3+>（m = au，ag）和rhombic- [pt_2cux（dpmp）_2]^<2+>（x = cl，br，i）。用Pt^0和Pd^0物种处理复合抗2的物种得到了PT-PT-PT和PT-PD-PT-PT A-FRAME簇。有趣的调节了额外金属的插入位置，这是由1和2的两个非磷酸单元的排列。二核和三核Plladium和dpmp的钼复合物也被制备并表征。