Synthesis, Structure, and Electrochemistry of the Dicluster Molecular Pincer [Pt3(μ-PBut2)3(CO)2]2(μ-1′,1′′

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• 作者：Alberto Albinati ; Federica Balzano ; Fabrizia Fabrizi de Biani ; Piero Leoni ; Gabriele Manca ; Lorella Marchetti ; Silvia Rizzato ; Gloria Uccello Barretta ; Piero Zanello
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：April 19, 2010
• 年：2010
• 卷：49
• 期：8
• 页码：3714-3720
• 全文大小：845K
• 年卷期：v.49,no.8(April 19, 2010)
• ISSN：1520-510X

文摘

The CuI catalyzed dehydro-halogenation of 1′,1′′′-diethynylbiferrocene and {Pt₃}Cl [{Pt₃} = Pt₃(μ-PBu^t₂)₃(CO)₂] (1:2 molar ratio) in diethylamine gives in high yields the bicluster derivative [{Pt₃}CC-(η⁵-C₅H₄)Fe(η⁵-C₅H₄)]₂, 3, in which two platinum triangles are connected by a diethynylbiferrocene spacer. In the structure of 3, confirmed by a diffractometric study, the two {Pt₃} fragments lie, perfectly eclipsed, on the same side of the biferrocenyl moiety; this folded structure is also preferred in solution, as suggested by NMR Diffusion Ordered Spectroscopy (DOSY) and 1D Rotating-frame Overhauser Enhancement (ROE) measurements. Compound 3 exhibits a rich redox behavior, with a crowded sequence of six one-electron oxidation processes, the electrode potentials of which have been evaluated by digital simulations. On the basis of a spectroelectrochemical study, the first two oxidations are assigned to the iron centers of the diferrocenyl unit and the subsequent four electrons are removed from the {Pt₃} units.