Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction. Issue 18 (9th January 2019)

• Record Type: Journal Article
• Authors: Gerschel, P.; Warm, K.; Farquhar, E. R.; Englert, U.; Reback, M. L.; Siegmund, D.; Ray, K.; Apfel, U.-P.
• Is Part Of: Dalton transactions. Volume 48:Issue 18(2019)
• Page Start: 5923
• Page End: 5932
• Publication Date: 2019-01-09
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt04740e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : N/S replacement in Ni-cyclam complexes highlights the importance of biologically relevant sulfur ligands in the CO2 and proton reduction. 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 CO2 via 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.