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

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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