Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France.
Institute of Chemistry, Academy of Sciences of Moldova, 3, Academiei str., Chisinau, MD 2028, Republic of Moldova.
Chemistry. 2018 Jun 21;24(35):8779-8786. doi: 10.1002/chem.201801155. Epub 2018 Jun 6.
The synthesis and characterization of a dinuclear bis(thiosemicarbazone) cobalt complex [Co L (NCS) ] is reported. This complex exhibits significant catalytic activity for hydrogen production in DMF by using triethylammonium (Et NHBF ) as the proton source. Cyclic voltammetry data allowed a maximum turnover frequency of 130 s for 1 m proton concentration to be determined. The catalytic nature of the process and the production of dihydrogen were confirmed by gas analysis during controlled potential electrolysis experiments. Quantum chemical calculations show that the complex displays a ligand-assisted metal-centered reactivity and supports a catalytic mechanism involving ligand-based reduction and protonation steps followed by metal-centered processes.
报道了双核双(硫代缩氨基甲酸盐)钴配合物[CoL(NCS)]的合成与表征。该配合物在以三乙铵(EtNHBF)作为质子源的 DMF 中表现出显著的产氢催化活性。循环伏安数据允许确定在 1m 质子浓度下的最大周转频率为 130s。通过控制电位电解实验中的气体分析证实了该过程的催化性质和氢气的产生。量子化学计算表明，该配合物表现出配体辅助的金属中心反应性，并支持涉及配体还原和质子化步骤以及随后的金属中心过程的催化机制。
