Monofunctionalized Cobaltocenium Compounds by Dediazoniation Reactions of Cobaltoceniumdiazonium Bis(hexafluorophosphate)

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• 作者：Stefan Vanicek ; Holger Kopacka ; Klaus Wurst ; Thomas Müller ; Christopher Hassenrück ; Rainer F. Winter ; Benno Bildstein
• 刊名：Organometallics
• 出版年：2016
• 出版时间：June 27, 2016
• 年：2016
• 卷：35
• 期：12
• 页码：2101-2109
• 全文大小：413K
• 年卷期：0
• ISSN：1520-6041

文摘

Monofunctionalized cobaltocenium salts are obtained for the first time from cobaltoceniumdiazonium bis(hexafluorophosphate) with various nucleophiles via Sandmeyer-type and related reactions. For successful conversions, reaction conditions are quite critical: either standard solution chemistry in nitromethane or solvent-free ball milling proved necessary, depending on the type of reactant. By this synthetic approach valuable synthons such as iodocobaltocenium and azidocobaltocenium salts are accessible that open up new vistas in cobaltocenium chemistry. Spectroscopic characterization by NMR, IR, HRMS, and single-crystal structure analysis as well as the results of electrochemical studies are reported. Derivatives with two reversible reductions show the expected relation of the half-wave potentials with the Hammett substituent parameter σ_p of the respective substituent with a slightly larger slope for the first reduction. The carboxylic acid (reductive deprotonation of the −COOH functionality), the iodo (protodehalogenation), and the azido derivatives undergo irreversible subsequent reactions after primary reduction.