Citation: Tao Mei, Dawei Yang, Linan Su, Baomin Wang, Jingping Qu. Construction of a low-valent thiolate-bridged dicobalt platform and its reactivity toward hydrogen activation and evolution[J]. Chinese Chemical Letters, ;2022, 33(5): 2477-2480. doi: 10.1016/j.cclet.2021.11.014 shu

Construction of a low-valent thiolate-bridged dicobalt platform and its reactivity toward hydrogen activation and evolution

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

yangdw@dlut.edu.cn

Received Date: 16 September 2021
Revised Date: 3 November 2021
Accepted Date: 3 November 2021
Available Online: 11 November 2021

Figures(4)

Low-valence transition metallic complexes have drawn longstanding attention due to their high reactivity toward catalytic transformation of various small molecules. Among these known complexes, the low-valence metal centres are commonly stabilized by neutral bulky ligands with strong electron-donating capacity. However, low-valence bimetallic complexes supported by anionic sulfur and cyclopentadienyl ligands are still difficult to obtain in high isolated yield. Herein, we report the synthesis and characterization of two scarce thiolate-bridged Co^ⅠCo^Ⅱ and Co^ⅠCo^Ⅰ complexes bearing sterically demanding ligands through two stepwise one-electron reduction processes. Interestingly, the Co^ⅠCo^Ⅱ complex can facilely promote the homolytic cleavage of dihydrogen across the short Co−Co metallic bond to give a Co^ⅡCo^Ⅲ dihydride bridged complex, which is capable of serving as a competent hydrogen atom transfer agent. Moreover, the anionic Co^ⅠCo^Ⅰ complex can trigger a stepwise hydrogen generation cycle involving several isolated and structurally well-characterized intermediates.
- Low-valence,
- Thiolate-bridged,
- Cobalt,
- Homolytic H₂ cleavage,
- Hydride,
- Hydrogen evolution
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