Synthesis, Characterization, and Electrochemical Studies on [1.1]Ferrocenophanes Containing Aluminum, Gallium, and Indium

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• 作者：Jö ; rg A. Schachner ; Grzegorz A. Orlowski ; J. Wilson Quail ; Heinz-Bernhard Kraatz ; and Jens Mü ; ller
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：January 9, 2006
• 年：2006
• 卷：45
• 期：1
• 页码：454 - 459
• 全文大小：124K
• 年卷期：v.45,no.1(January 9, 2006)
• ISSN：1520-510X

文摘

The synthesis, characterization, structure, and electrochemistry of [1.1]ferrocenophanes, bridged by the heaviergroup 13 elements aluminum (1a), gallium (1b), and indium (1c), are described and discussed. Compounds 1a-chave been synthesized from dilithioferrocene and intramolecularly coordinated group 13 element dihalides Ar'EX₂(Ar' = 2-(Me₂NCH₂)C₆H₄; EX₂ = AlCl₂, GaCl₂, InI₂). Although the synthesis and characterization of 1a by single-crystal X-ray analysis has been described recently (Braunschweig, H.; Burschka, C.; Clentsmith, G. K. B.; Kupfer,T.; Radacki, K. Inorg. Chem. 2005, 44, 4906), compounds 1b and 1c are described for the first time. The galla (1b)and the inda (1c) [1.1]ferrocenophane have been characterized by single-crystal X-ray determination [1b: C₃₈H₄₀Fe₂Ga₂N₂, monoclinic, P2₁/c, a = 10.3467(5) Å, b = 11.6311(4) Å, c = 14.0747(7) Å, ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 105.931(2)ages/entities/deg.gif">, Z = 2;1c: C₃₈H₄₀Fe₂In₂N₂, monoclinic, P2₁/c, a = 10.5522(7) Å, b = 11.8476(8) Å, c = 13.9855(9) Å, ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 104.990(3)ages/entities/deg.gif">,Z = 2]. All three compounds 1a-c are anti conformers with trans orientations of the two donating NMe₂ groups.For the [1.1]ferrocenophane 1a, an unprecedented fully reversible two-electron redox process was observed bycyclic voltammetry, whereas the corresponding Ga and In species exhibit a more conventional stepwise redoxchemistry. According to the Robin-Day classification, 1a is a class I and 1b and 1c are class II species. In additionto the reversible processes, compound 1a shows an irreversible oxidation at higher voltages accompanied byadsorption processes. The irreversible adsorption process was investigated with an electrochemical quartz crystalmicrobalance (EQCM).