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Anodic oxidation of ethynylferrocene derivatives in homogeneous solution and following anodic deposition onto glassy carbon electrodes

Anodic oxidation of ethynylferrocene derivatives in homogeneous solution and following anodic deposition onto glassy carbon electrodes

Geiger, William E, Sheridan, Matthew V, Lam, Kevin ORCID: 0000-0003-1481-9212 and Waterman, Rory (2019) Anodic oxidation of ethynylferrocene derivatives in homogeneous solution and following anodic deposition onto glassy carbon electrodes. ChemElectrochem, 6 (23). pp. 5880-5887. ISSN 2196-0216 (Online) (doi:https://doi.org/10.1002/celc.201901545)

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Abstract

Eight ferrocene derivatives linked by either an ether, amine, or phenylacetylene moiety to a terminal ethynyl group were covalently deposited on glassy carbon electrodes by anodic electrochemical methods. The lithio activation method, in which the terminal hydrogen of the ethynyl group is replaced by a lithium atom before anodic oxidation, was successfully employed in all cases. Direct oxidation of the unactivated ethynyl group also resulted in surface deposition. Surface coverages between 1 x 10 ‐10 mol cm ‐2 and 14 x 10 ‐10 mol cm ‐2 were achieved. Cyclic voltammetry scans of the modified electrodes in pure electrolytes differed depending on the size of the supporting electrolyte anion, as little as half the current being measured for a [B(C 6 F 5 ) 4 ] ‐ vs. [PF 6 ] ‐ solution, suggesting differences in ion transport near the electrode surface. An ether‐linked ethynylferrocenium ion ( 5 + ) was isolated after electrolytic and chemical oxidation of 5 and characterized by X‐Ray crystallography as its [SbCl 6 ] ‐ salt.

Item Type: Article
Uncontrolled Keywords: electrochemistry, surface modification, organometallics
Subjects: Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science
Faculty of Engineering & Science > School of Science (SCI)
Last Modified: 31 Jan 2020 12:37
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
Selected for GREAT 2019: None
URI: http://gala.gre.ac.uk/id/eprint/25980

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