title: Anodic Methods for Covalent Attachment of Ethynylferrocenes to Electrode Surfaces: Comparison of Ethynyl Activation Processes.
abstract: The electrochemical oxidation of ferrocenes having an H- or Li-terminated ethynyl group has been studied, especially as it relates to their covalent anchoring to carbon surfaces. The anodic oxidation of lithioethynylferrocene (1-Li) results in rapid loss of Li(+) and formation of the ethynyl-based radical FeCp(η(5)-C5H4)(C≡C), (1, Cp = η(5)-C5H5), which reacts with the electrode. Chemically modified electrodes (CMEs) were thereby produced containing strongly bonded, ethynyl-linked monolayers and electrochemically controlled multilayers. Strong attachments of ethynylferrocenes to gold and platinum surfaces were also possible. The lithiation/anodic oxidation process is a mirror analogue of the diazonium/cathodic reduction process for preparation of aryl-modified CMEs. A second method produced an ethynylferrocene-modified electrode by direct anodic oxidation of the H-terminated ethynylferrocene (1-H) at a considerably more positive potential. Both processes produced robust modified electrodes with well-defined ferrocene-based surface cyclic voltammetry waves that remained unchanged for as many as 10(4) scans. Ferrocene derivatives in which the ethynyl moiety was separated from the cyclopentadienyl ring by an ether group showed very similar behavior. DFT calculations were performed on the relevant redox states of 1-H, 1-Li, and 1, with emphasis on the ferrocenyl vs ethynyl character of their high valence orbitals. Whereas the HOMOs of both 1-H and 1-Li have some ethynyl character, the SOMOs of the corresponding monocations are strictly ferrocenium in makeup. Predominant ethynyl character returns to the highest valence orbitals after loss of Li(+) from [1-Li](+) or loss of H(+) from [1-H](2+). These anodic processes hold promise for the controlled chemical modification of carbon and other electrode surfaces by a variety of ethynyl or alkynyl-linked organic and metal-containing systems.
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
authors.forename: Matthew V
authors.initials: MV
authors.lastname: Sheridan
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
authors.forename: Kevin
authors.initials: K
authors.lastname: Lam
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
authors.forename: Mona
authors.initials: M
authors.lastname: Sharafi
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
authors.forename: Severin T
authors.initials: ST
authors.lastname: Schneebeli
authors.affiliation: Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.
authors.forename: William E
authors.initials: WE
authors.lastname: Geiger