Eine konvergente Route zu metallorganischen Dendrimeren aus Platin-Acetylid-Einheiten

Transition-metal s-alkynyl derivatives [1] are emerging as potentially useful precursors for advanced materials due to their promising magnetic, [2] liquid-crystalline, [3] nonlinear optical, [4] and luminescence [5] properties. Moreover, there is considerable and increasing interest for their application in the synthesis of metal-containing macrocyclic, [6] dendritic, [7] and rigid-rod molecular frameworks with delocalized p systems. These compounds include derivatives of various dimensions, actively investigated for their potential use in molecular electronics, [8,9] and contain isolated metal centers either located at the extremes [8][9][10][11] or regularly intercalated [8,12] into the main chain. Ordered structures with alternated metal clusters (or metal-metal-bonded bimetallic units [13] ) and conjugated s-alkynyl spacers [14][15] are extremely rare, [16] although of great potential interest. [10] This may be due to: 1) the tendency of metal clusters to undergo fragmentation or condensation, 2) their multiple and undistinguishable reactive positions, which facilitate the formation of complex mixtures of products, and 3) the preferred p interaction between the cluster and the alkynyl units [1,17] (the metal-alkynyl s linkage usually results in increased electronic delocalization [9] ). In this paper we show that tri-and hexanuclear platinum clusters with sizable bridging phosphide groups are suitable precursors to ordered materials. Indeed, the bulky PtBu 2 ligands in [Pt 3 (m-PtBu 2 ) 3 (L) 2 (X)]n+ [18] and [Pt 6 (m-PtBu 2 ) 4 -(CO) 4 (X) 2 ]2n+ [19] (X = neutral ligand, n = 1; X = monoanionic ligand, n = 0; L = neutral ligand) impart remarkable thermal and chemical stability to the {Pt x (m-P) y } cores and leave a limited number of reactive sites properly positioned to build ordered structures. Moreover, they force alkynyl ligands to bind the polynuclear system with s,h 1 -rather than p,h 2 -interactions.[20] Several structures with predefined molecular shape can therefore be engineered through the combination of these building blocks with well-chosen s-alkynyl spacers, one of which is shown in Scheme 1. The trinuclear precursor Scheme 1. Synthesis of complex 6. i) 1,3,5-C 6 H 3 (CCH) 3 , CuI, NEt 2 H, 25 8C, 24 h (80 %); ii) 3 (2 equiv), 5, CuI, NEt 2 H, 25 8C, 24 h (85 %) (5 = [Pt 6 (m-PtBu 2 ) 4 (CO) 4 Cl 2 ]).

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Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Albinati

Leoni

Marchetti

et al. 2003

Angewandte Chemie

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Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

et al. 2003

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Convergent Synthesis of Platinum–Acetylide Dendrimers

Onitsuka

Fujimoto

Kitajima

et al. 2004

Chemistry A European J

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An efficient convergent route to the main chain type of organometallic dendrimers, in which platinum moieties are linked by 1,3,5-triethynylbenzene, has been developed. The synthesis of platinum-acetylide dendrons involved the use of two types of trialkylsilyl groups for protection of the terminal acetylene. The platinum-acetylide dendrimers were prepared up to the third generation by reacting dendrons with a triplatinum core and a tetraplatinum core. Spectroscopic characterization and trace experiments by gel permeation chromatography indicated that the dendrimer molecules have no structural defects. Although a pi-conjugated system was used as the bridging ligand, electronic and fluorescence spectra suggested that the interaction among the platinum-acetylide moieties in the dendrimers was small.

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Eine konvergente Route zu metallorganischen Dendrimeren aus Platin-Acetylid-Einheiten

Cited by 5 publications

References 28 publications

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Convergent Synthesis of Platinum–Acetylide Dendrimers

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Eine konvergente Route zu metallorganischen Dendrimeren aus Platin-Acetylid-Einheiten

Cited by 5 publications

References 28 publications

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt18 Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt18 Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt18 Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Convergent Synthesis of Platinum–Acetylide Dendrimers

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Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers

Assembling Metal Clusters with Covalent Linkers: Synthesis and Structure of a Quasi‐Planar Pt₁₈ Dendrimer Containing Five Clusters Connected by σ‐Alkynyl Spacers