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Addressing the Reproducibility of Photocatalytic Carbon Dioxide Reduction

2019, Marx, Maximilian, Mele, Andrea, Spannenberg, Anke, Steinlechner, Christoph, Junge, Henrik, Schollhammer, Philippe, Beller, Matthias

Reproducibility of photocatalytic reactions, especially when conducted on small scale for improved turnover numbers with in situ formed catalysts can prove challenging. Herein, we showcase the problematic reproducibility on the example of attractive photocatalytic CO2 reduction utilizing [FeFe] hydrogenase mimics. These Fe complexes, well-known for their application in proton reduction reactions, were combined with a heteroleptic Cu photosensitizer and produced CO/H2/HCO2H mixtures of variable constitution. However, the reactions indicated a poor reproducibility, even when conducted with well-defined complexes. Based on our experience, we make suggestions for scientists working in the field of photocatalysis on how to address and report the reproducibility of novel photocatalytic reaction protocols. In addition, we would like to highlight the importance of studying reproducibility of novel reaction protocols, especially in the fields of photocatalytic water splitting and CO2 reduction, where TONs are widely used as the comparable measure for catalytic activity. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid

2019, Zhou, Wei, Wei, Zhihong, Spannenberg, Anke, Jiao, Haijun, Junge, Kathrin, Junge, Henrik, Beller, Matthias

Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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Tetra­carbon­yl[4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline-κ2N,N′]molybdenum(0)

2019, Steinlechner, Christoph, Spannenberg, Anke, Junge, Henrik, Beller, Matthias

In the title compound, [Mo(C10H12N2O)(CO)4], the molybdenum(0) center is surrounded by a bidentate di­imine [4,4-dimethyl-2-(pyridin-2-yl)-2-oxazoline] and four carbonyl ligands in a distorted octa­hedral coordination geometry. The di­imine ligand coordinates via the two nitro­gen atoms.