Charge Transfer Properties of Multi(ferrocenyl)trindenes

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• 作者：Alessandro Donoli ; Annalisa Bisello ; Roberta Cardena ; Cristina Prinzivalli ; Saverio Santi
• 刊名：Organometallics
• 出版年：2013
• 出版时间：February 25, 2013
• 年：2013
• 卷：32
• 期：4
• 页码：1029-1036
• 全文大小：374K
• 年卷期：v.32,no.4(February 25, 2013)
• ISSN：1520-6041

文摘

Ferrocenyl, diferrocenyl, and triferrocenyl complexes of dihydro-1H-trindene have been prepared by up to 3-fold bromide substitution of the dihydro-2,5,8-tribromo-1H-trindene halocarbon. The charge transfer properties of their mono-, di-, and tricationic derivatives were investigated. The cations of this new family of multi(ferrocenyl)trindene complexes were generated by chemical oxidation using (acetylferrocenium)(BF₄) as the oxidative agent and monitored in the visible, IR and near-IR regions. The charge transfer bands in the near-IR spectra are rationalized in the framework of the Marcus鈥揌ush theory. In particular, the triferrocenyl complexes display a redox chemistry that can be switched from a unresolved three-electron oxidation to two consecutive one-electron and two near simultaneously occurring one-electron oxidations by changing the supporting electrolyte from [nBu₄N][PF₆] to [nBu₄][B(C₆F₅)₄]. In addition, the introduction of the third ferrocenyl group increases the strength of the metal鈥搈etal interaction with respect to that of the structurally related diferrocenyl system.