The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

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• 作者：Michael S. Inkpen ; Shuoren Du ; Mariana Hildebrand ; Andrew J. P. White ; Nicholas M. Harrison ; Tim Albrecht ; Nicholas J. Long
• 刊名：Organometallics
• 出版年：2015
• 出版时间：November 23, 2015
• 年：2015
• 卷：34
• 期：22
• 页码：5461-5469
• 全文大小：421K
• ISSN：1520-6041

文摘

We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1鈥?dihaloferrocene (fcX₂) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1鈥?diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1鈥?difluoroferrocene (fcF₂) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1鈥?dichloroferrocene (fcCl₂), were utilized as model systems to probe the limits of a previously reported 鈥渙xidative purification鈥?methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX₂ series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.