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

该项目的一个主要目的是通过与π偶联有机接头订购组装金属金属小型过渡金属簇来开发新的功能分子设备。我们已经（1）将零价铂和钯碎片的现场选择性合并到外交原理中，并由三磷蛋白配体支撑，形成了线性三分之一的三分之一的三分之一，（2）通过EHMO和DFT方法对三分之一的复合物进行了simerec complections（3）探索，并探索了新的（3）探索，并探索了新的（3）。（4）三latinum络合物和组装三丁基单位的终末配体交换反应，通过使用双异氰酯配体。 D22（μ-DPMP）IID22（RNC）IID22] IID12+IID1（1和2）。 1（SYN）和2（抗）的差异反应性允许访问多功能聚合……更多的HOMO和HETRO TRINACLEAL簇。前者通过DHIID110IID1PTWIID10IID1，PDWIID10IID1，AUID1IID1和CUID1IID1和D18 D1PTWITTER D1III D1，PDWITTER D1II D1，PDWITTER D1III D1III D1，IR D1III D1，IR D1III D1，和RHH D1II D1II d1 vive forver prevever。用PTWITTER D10 D1和PDWITTER D10 D1片段对复合物2的处理得到了PT-M-PT A-FRAME簇（M = PT，PD）。额外金属的插入位置很有趣，取决于起始外交综合体的两个DPMP布置。还进行了钯，黄金和钼簇的相应化学。由于金属 - 金属键合的三肽复合物，线性 - [PTWILL D23E D2（μ-DPMP）D22E D2（Xylnc）D22E D2]（PF）D22E D2] D222E D2）D2（6）被认为是与金属催化物的最小模型，其与各种有机分子的表面被认为是最小的模型。此外，线性 - 普特d23e D2单位的一维组合是由6种与各种芳族双异丝苷配体的反应建立的。较少的