A vitamin B-12 derivative, heptapropyl cobyrinate perchlorate, was readily trapped onto an indium tin oxide (ITO) electrode by a sol-gel reaction. The complex was physically retained in a silica gel film which is formed on an ITO electrode. The thickness of the film could be controlled by the withdrawing speed of the dip coating process. Formation of a sol-gel film was confirmed by SEM measurements, and the total amount of the complex in the film was determined by UV-VIS absorption spectra. The complex exhibits the Co-II/Co-I redox couple at -0.42 V vs. Ag-AgCl. The amount of the electroactive complex in the sol-gel film deduced from electrochemical measurements is 3.0 x 10(-11) and 6.2 x 10(-11) mol cm(-2) for thicknesses of 170 and 330 nm, respectively. This electroactive complex shows a high reactivity towards organic halides, and the controlled-potential electrolysis of benzyl bromide using the sol-gel modified electrode at -1.20 V vs. Ag-AgCl in aqueous solution containing 0.1 M KCl afforded dehalogenated products, bibenzyl and toluene, with a total turnover number of >1000 for 1 h.
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