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Gerschel P, Warm K, Farquhar ER, et al. Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO. Dalton Trans. 2019;48(18):5923-5932doi: 10.1039/c8dt04740e.
Gerschel, P., Warm, K., Farquhar, E. R., Englert, U., Reback, M. L., Siegmund, D., Ray, K., & Apfel, U. P. (2019). Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO. Dalton transactions (Cambridge, England : 2003), 48(18), 5923-5932. https://doi.org/10.1039/c8dt04740e
Gerschel, P, et al. "Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO." Dalton transactions (Cambridge, England : 2003) vol. 48,18 (2019): 5923-5932. doi: https://doi.org/10.1039/c8dt04740e
Gerschel P, Warm K, Farquhar ER, Englert U, Reback ML, Siegmund D, Ray K, Apfel UP. Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO. Dalton Trans. 2019 May 07;48(18):5923-5932. doi: 10.1039/c8dt04740e. PMID: 30624449; PMCID: PMC6504587.
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Dalton Trans. 2019 May 07;48(18):5923-5932. doi: 10.1039/c8dt04740e.

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO.

Dalton transactions (Cambridge, England : 2003)

P Gerschel, K Warm, E R Farquhar, U Englert, M L Reback, D Siegmund, K Ray, U-P Apfel

Affiliations

  1. Ruhr-Universität Bochum, Anorganische Chemie I, Universitätsstraße 150, 44801 Bochum, Germany. [email protected].

PMID: 30624449 PMCID: PMC6504587 DOI: 10.1039/c8dt04740e

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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