Electrochemical CO\(_2\) and proton reduction by a Co(dithiacyclam) complex
- While [Ni(cyclam)]\(^{2+}\) and [Ni(dithiacyclam)]\(^{2+}\) complexes were shown to be potent electrocatalysts for the CO\(_2\) conversion, their respective Co complexes hitherto received only little attention. Herein, we report on the CoII complexes of the cyclam and dithiacyclam platform, describe their synthesis and reveal their rich solvent dependent coordination chemistry. We show that sulfur implementation into the cyclam moiety leads to a switch from a low spin CoII complex in [Co(cyclam)]\(^{2+}\) to a high spin form in [Co(dithiacyclam)]\(^{2+}\). Notably, while both complexes are capable to perform the reduction of CO\(_2\) to CO, H\(_2\) formation is generally preferred. Along this line, the complexes were shown to enable proton reduction from acetic acid. However, in comparison to [Co(cyclam)]\(^{2+}\), the altered electronics make [Co(dithiacyclam)]\(^{2+}\) complexes prone to deposit on the glassy carbon working electrode over time leading to an overall low faradaic efficiency for the reduction of protons or CO\(_2\).
| Author: | Linda IfflandGND, Daniel SiegmundORCiDGND, Ulf-Peter ApfelORCiDGND |
|---|---|
| URN: | urn:nbn:de:hbz:294-83653 |
| DOI: | https://doi.org/10.1002/zaac.201900356 |
| Parent Title (English): | Zeitschrift für anorganische und allgemeine Chemie |
| Publisher: | Wiley-VCH Verlag |
| Place of publication: | Weinheim |
| Document Type: | Article |
| Language: | English |
| Date of Publication (online): | 2021/10/07 |
| Date of first Publication: | 2020/02/28 |
| Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
| Tag: | Carbon dioxide; Dithiacyclam; Electrocatalysis; Hydrogen |
| GND-Keyword: | Cobalt |
| Volume: | 646 |
| Issue: | 13 |
| First Page: | 746 |
| Last Page: | 753 |
| Note: | Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich. |
| Institutes/Facilities: | Lehrstuhl für Anorganische Chemie I, Aktivierung kleiner Moleküle |
| open_access (DINI-Set): | open_access |
| faculties: | Fakultät für Chemie und Biochemie |
| Licence (English): |  Creative Commons - CC BY 4.0 - Attribution 4.0 International |
