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Nano-Scale Design of Metal-Metal Bonded Transition Metal Clusters and Their Assemblage with an Aim of Multifunctionarity

以多功能为目标的金属-金属键合过渡金属簇及其组装的纳米级设计

基本信息

批准号：
09554038
负责人：
TANASE Tomoaki
金额：
$ 6.21万
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 (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

A main aim of this project is developing new functional molecular devices by ordered assembling metal-metal bonded small-size transition metal clusters with π-conjugated organic linkers. We have carried out (1)full investigation of site-selective incorporation of zero-valent platinum and palladium fragments into diplatinum centers supported by a triphosphine ligand forming the linear triplatinum complex, (2)molecular orbital calculations with EHMO and DFT methods on the triplatinum complex, (3)exploration of new reactions of the triplatinum complex with small molecules, and (4)terminal ligand exchange reactions of the triplatinum complex and assembling triplatinum units by utilizing bisisocyanide ligands.Reaction of [PtィイD22ィエD2(RNC)ィイD26ィエD2]ィイD12+ィエD1 (RNC = aromatic isocyanide) with dpmp afforded an isomeric mixture of syn- and anti-[PtィイD22ィエD2(μ-dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 (1 and 2). The differential reactivity of 1(syn) and 2(anti) allows an access to versatile aggreg … More ations of homo and hetero trinuclear clusters. The former was transformed by treatment with dィイD110ィエD1PtィイD10ィエD1, PdィイD10ィエD1, AuィイD1IィエD1, AgィイD1IィエD1, and CuィイD1IィエD1 and dィイD18ィエD1PtィイD1IIィエD1, PdィイD1IIィエD1, IrィイD1IィエD1, and RhィイD1IィエD1 species to a wide variety of Pt-Pt-M clusters. Treatment of complex 2 with PtィイD10ィエD1 and PdィイD10ィエD1 fragments gave Pt-M-Pt A-frame clusters (M = Pt, Pd). The inserted position of the additional metal is interestingly depends on the two dpmp arrangement of the starting diplatinum complexes. The corresponding chemistry of palladium, gold and molybdenum clusters was also carried out. Since the metal-metal bonded triplatinum complex, linear-[PtィイD23ィエD2(μ-dpmp)ィイD22ィエD2(XylNC)ィイD22ィエD2](PFィイD26ィエD2)ィイD22ィエD2 (6) was regarded as a minimal model for the surface of metal catalyst, its reactions with various small organic molecules were examine. Further, one-dimensional assemblage of linear-PtィイD23ィエD2 units was established by the reactions of 6 with various aromatic bisisocyanide ligands. Less

本项目的主要目标是通过有序组装金属-金属键合的小尺寸过渡金属簇与π共轭有机连接体来开发新的功能分子器件。我们进行了（1）三膦配体支持的双铂中心上的零价铂和钯片段的位置选择性嵌入形成线性三铂配合物的全面研究，（2）三铂配合物的EHMO和DFT分子轨道计算，（3）三铂配合物与小分子的新反应探索，（4）三铂配合物的末端配体交换反应，利用双异氰配体组装三铂单元。[Pt D22 D2（RNC）D26 D2] D12+ D1的反应（RNC =芳族异氰化物）与dpmp反应，得到顺式和反式[Pt（CN）D22 CN D2（μ-dpmp）CN D22 CN D2（RNC）CN D22 CN D2] CN D12+ CN D1的异构体混合物（1和2）。1（顺式）和2（反式）的不同反应性允许获得多功能聚集体， ...更多信息同三核和异三核簇合物。前者通过用d-Pt D110-Pt D1-Pt D10-Pt D1-Pt D配合物2与Pt_（10）Pd_（10）Pt_（10）Pd_（10）Pt_（10）反应，得到Pt-M-Pt A-骨架簇合物（M = Pt，Pd）。有趣的是，附加金属的插入位置取决于起始双铂络合物的两个dpmp排列。还进行了钯、金和钼簇合物的相应化学研究。由于金属-金属键合的三铂络合物线性-[Pt <$D23 <$D22 <$D22（μ-dpmp）<$D22 <$D22（XylNC）<$D22 <$D22]（PF <$D26 <$D22）<$D22 <$D22（6）被认为是金属催化剂表面的最小模型，因此考察了它与各种有机小分子的反应。此外，一维组装的线性-Pt D23 D2单元建立了6与各种芳香族bisisocyanide配体的反应。少