ROMP Synthesis and Redox Properties of Polycationic Metallopolymers Containing the Electron-Reservoir Complex [Fe(畏5-C5H5)(畏6-C6Me6)][

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• 作者：Haibin Gu ; Roberto Ciganda ; Ricardo Hernandez ; Patricia Castel ; Pengxiang Zhao ; Jaime Ruiz ; Didier Astruc
• 刊名：Macromolecules
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：48
• 期：17
• 页码：6071-6076
• 全文大小：285K
• ISSN：1520-5835

文摘

Electron-reservoir metallopolymers in which these nanomaterials are robust in at least two oxidation states are being actively investigated in view of applications as stable electron-transfer reagents. Here living ring-opening metathesis polymerization (ROMP) and diblock copolymerization of norbornene derivatives are conducted in which the cationic organoiron complex [FeCp(畏⁶-C₆Me₆)][PF₆] (Cp = 畏⁵-C₅H₄R) is covalently attached to the norbornene motif with a short trimethylene amido linker or a longer linker containing also the triethylene glycol (TEG) unit. Solubility constraints involved with the shorter linker require that the ROMP reaction be conducted in dimethylformamide (DMF), whereas the solubilizing longer linker conveniently allows carrying out the ROMP reaction in dichloromethane (DCM). Cyclic voltammetry (CV) of all these metallopolymers shows the full reversibility of the Fe^II 鈫?Fe^I reduction wave at 鈭?.35 V vs decamethylferrocene, [FeCp*₂], and the numbers of monomer units found using the Bard鈥揂nson method by CV are close to the monomer/catalyst ratio used in the ROMP reaction.