Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis
Co bis(benzenedithiolate) type complexes have captivated chemists for decades for their interesting geometric and electronic structures and more recently, for their impressive ability to mediate the hydrogen evolution reaction (HER) both photo- and electrocatalytically. However, these complexes have...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-02-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/12/3/75 |
| _version_ | 1827306005357133824 |
|---|---|
| author | Virginia A. Larson Jeff W. Kampf Nicolai Lehnert |
| author_facet | Virginia A. Larson Jeff W. Kampf Nicolai Lehnert |
| author_sort | Virginia A. Larson |
| collection | DOAJ |
| description | Co bis(benzenedithiolate) type complexes have captivated chemists for decades for their interesting geometric and electronic structures and more recently, for their impressive ability to mediate the hydrogen evolution reaction (HER) both photo- and electrocatalytically. However, these complexes have nearly exclusively been characterized in their air-stable Co(III) oxidation states. In this work, Co(II) bis(benzenedichlorodithiolate) was prepared by chemical and electrochemical one-electron reduction. This reduced Co(II) complex was characterized by X-ray crystallography and in-depth spectroscopic studies—including UV-Vis, magnetic circular dichroism, and electron paramagnetic resonance spectroscopy. [Co(II)(Cl<sub>2</sub>bdt)<sub>2</sub>]<sup>2−</sup> is thereby shown to be a square planar complex, with a primarily metal-centered reduction, and an <i>S</i><sub>t</sub> = 1/2 spin state. This study informs our understanding of the first step in the HER catalytic cycle of Co bis(benzenedithiolate) type complexes and paves the way for future mechanistic studies on this catalyst family. |
| first_indexed | 2024-04-24T18:10:45Z |
| format | Article |
| id | doaj.art-d8548cdbad1143d6b8dacf618f6601c2 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-04-24T18:10:45Z |
| publishDate | 2024-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-d8548cdbad1143d6b8dacf618f6601c22024-03-27T13:47:05ZengMDPI AGInorganics2304-67402024-02-011237510.3390/inorganics12030075Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution CatalysisVirginia A. Larson0Jeff W. Kampf1Nicolai Lehnert2Department of Chemistry and Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055, USADepartment of Chemistry and Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055, USADepartment of Chemistry and Department of Biophysics, University of Michigan, Ann Arbor, MI 48109-1055, USACo bis(benzenedithiolate) type complexes have captivated chemists for decades for their interesting geometric and electronic structures and more recently, for their impressive ability to mediate the hydrogen evolution reaction (HER) both photo- and electrocatalytically. However, these complexes have nearly exclusively been characterized in their air-stable Co(III) oxidation states. In this work, Co(II) bis(benzenedichlorodithiolate) was prepared by chemical and electrochemical one-electron reduction. This reduced Co(II) complex was characterized by X-ray crystallography and in-depth spectroscopic studies—including UV-Vis, magnetic circular dichroism, and electron paramagnetic resonance spectroscopy. [Co(II)(Cl<sub>2</sub>bdt)<sub>2</sub>]<sup>2−</sup> is thereby shown to be a square planar complex, with a primarily metal-centered reduction, and an <i>S</i><sub>t</sub> = 1/2 spin state. This study informs our understanding of the first step in the HER catalytic cycle of Co bis(benzenedithiolate) type complexes and paves the way for future mechanistic studies on this catalyst family.https://www.mdpi.com/2304-6740/12/3/75Co bis(benzenedithiolate) complexeshydrogen evolution reactionreaction intermediatesenergyelectrocatalysis |
| spellingShingle | Virginia A. Larson Jeff W. Kampf Nicolai Lehnert Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis Inorganics Co bis(benzenedithiolate) complexes hydrogen evolution reaction reaction intermediates energy electrocatalysis |
| title | Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis |
| title_full | Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis |
| title_fullStr | Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis |
| title_full_unstemmed | Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis |
| title_short | Structural and Spectroscopic Characterization of Co(II) Bis(Benzenedichlorodithiolate): An Intermediate in Hydrogen Evolution Catalysis |
| title_sort | structural and spectroscopic characterization of co ii bis benzenedichlorodithiolate an intermediate in hydrogen evolution catalysis |
| topic | Co bis(benzenedithiolate) complexes hydrogen evolution reaction reaction intermediates energy electrocatalysis |
| url | https://www.mdpi.com/2304-6740/12/3/75 |
| work_keys_str_mv | AT virginiaalarson structuralandspectroscopiccharacterizationofcoiibisbenzenedichlorodithiolateanintermediateinhydrogenevolutioncatalysis AT jeffwkampf structuralandspectroscopiccharacterizationofcoiibisbenzenedichlorodithiolateanintermediateinhydrogenevolutioncatalysis AT nicolailehnert structuralandspectroscopiccharacterizationofcoiibisbenzenedichlorodithiolateanintermediateinhydrogenevolutioncatalysis |