Catalysis Group, Department of Chemistry, Indian Institute of Technology Indore, Simrol, Indore 453552, Madhya Pradesh, India.
Computational Materials Designing Group, Department of Chemistry, Indian Institute of Technology Indore, Simrol, Indore 453552, Madhya Pradesh, India.
Inorg Chem. 2023 May 29;62(21):8080-8092. doi: 10.1021/acs.inorgchem.2c04079. Epub 2023 May 17.
Diruthenium complexes [{(η-arene)RuCl}(μ-κ:κ-benztetraimd)] containing the bridging bis-imidazole methane-based ligand {1,4-bis(bis(2-ethyl-5-methyl-1-imidazol-4-yl)methyl)benzene} (benztetraimd) are synthesized for catalytic formic acid dehydrogenation in water at 90 °C. Catalyst [{(η--cymene)RuCl}(μ-κ:κ-benztetraimd)] exhibited a remarkably high turnover frequency (1993 h per Ru atom) and long-term stability over 60 days for formic acid dehydrogenation, while the analogous (η-benzene)diruthenium and mononuclear catalysts displayed low activity with poor long-term stability. Notably, catalyst also displayed an appreciably high turnover number of 93 200 for the bulk-scale reaction. In addition, the in-depth mass and nuclear magnetic resonance investigations under the catalytic and control experimental conditions revealed the active involvement of several crucial catalytic intermediate species, such as Ru-aqua species [{(η--cymene)Ru(HO)}(μ-L)] , Ru-formato species [{(η--cymene)Ru(HCOO)}(μ-L)] -, and Ru-hydrido species [{(η--cymene)Ru(H)}(μ-L)] , in the catalytic formic acid dehydrogenation reaction.
含有桥联双咪唑甲烷配体{1,4-双（双（2-乙基-5-甲基-1-咪唑-4-基）甲基）苯}（benztetraimd）的二钌配合物[{（η-芳烃）RuCl}（μ-κ：κ-benztetraimd）}被合成用于在 90°C 的水中催化甲酸脱氢。催化剂[{（η--环戊二烯）RuCl}（μ-κ：κ-benztetraimd）]在甲酸脱氢反应中表现出非常高的周转频率（每个 Ru 原子 1993 h）和 60 天以上的长期稳定性，而类似的（η-苯）二钌和单核催化剂的活性较低，长期稳定性差。值得注意的是，催化剂[也在大规模反应中表现出相当高的 93200 个转化数。此外，在催化和对照实验条件下的深入质量和核磁共振研究揭示了几种关键催化中间物种的积极参与，例如 Ru-水合物种[{（η--环戊二烯）Ru（HO）}（μ-L）]，Ru-甲酸盐物种[{（η--环戊二烯）Ru（HCOO）}（μ-L）]-和 Ru-氢化物物种[{（η--环戊二烯）Ru（H）}（μ-L）]，在催化甲酸脱氢反应中。
