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Published on: September 22, 2015
Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton
P Gerschel1, K Warm, E R Farquhar
1Ruhr-Universität Bochum, Anorganische Chemie I, Universitätsstraße 150, 44801 Bochum, Germany. ulf.apfel@rub.de.
Abstract:
The replacement of the opposing nitrogen atoms in 1,4,8,11-tetraazacyclotetradecane (cyclam) with two sulfur atoms in 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam) enables the electrochemical reduction of protons and CO2via the corresponding nickel(ii) complex at more positive potentials. In addition, a 10-fold enhancement in the proton reduction rate of [Ni(dithiacyclam)]2+ relative to [Ni(cylcam)]2+ was observed. The study provides vital insight into Nature's choice of employing predominantly sulfur based ligand platforms in achieving biological proton and CO2 reductions.
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