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-金属键合的小尺寸铂和钯簇作为多相催化剂表面的最小模型越来越受到人们的关注；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。报道了通过二铂前驱体与双（二苯基膦甲基）苯基膦（dpmp）系统合成同质和异质三金属铂簇。 [Pt_2(RNC)_6]^<2+> (RNC=芳族异氰化物)与dpmp的反应提供了顺式和反式[Pt_2(dpmp)_2(RNC)_2]^<2+>的异构体混合物( syn-1 和 anti-2)。 syn-1 和 anti-2 的不同反应性允许获得同源和异源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 和 Cu 处理进行转化^I 种类为多种 Pt-Pt-M 簇，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)，Y形-[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 物质处理复合物抗 2，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通过两个不协调的膦单元 1 和 2 的排列来调节。还制备并表征了二核和三核钯和钼与 dpmp 的配合物。