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Reactivity of Metal Catalysts in Glucose–Fructose Conversion

MPS-Authors
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Loerbroks,  Claudia
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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van Rijn,  Jeaphianne
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Ruby,  Marc-Philipp
Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Tong,  Qiong
Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Schüth,  Ferdi
Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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chem_201402437_sm_miscellaneous_information.pdf
(Supplementary material), 3MB

Citation

Loerbroks, C., van Rijn, J., Ruby, M.-P., Tong, Q., Schüth, F., & Thiel, W. (2014). Reactivity of Metal Catalysts in Glucose–Fructose Conversion. Chemistry - A European Journal, 20(38), 12298-12309. doi:10.1002/chem.201402437.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0024-07E5-F
Abstract
A joint experimental and computational study on the glucose–fructose conversion in water is reported. The reactivity of different metal catalysts (CrCl3, AlCl3, CuCl2, FeCl3, and MgCl2) was analyzed. Experimentally, CrCl3 and AlCl3 achieved the best glucose conversion rates, CuCl2 and FeCl3 were only mediocre catalysts, and MgCl2 was inactive. To explain these differences in reactivity, DFT calculations were performed for various metal complexes. The computed mechanism consists of two proton transfers and a hydrogen-atom transfer; the latter was the rate-determining step for all catalysts. The computational results were consistent with the experimental findings and rationalized the observed differences in the behavior of the metal catalysts. To be an efficient catalyst, a metal complex should satisfy the following criteria: moderate Brønsted and Lewis acidity (pKa=4–6), coordination with either water or weaker σ donors, energetically low-lying unoccupied orbitals, compact transition-state structures, and the ability for complexation of glucose. Thus, the reactivity of the metal catalysts in water is governed by many factors, not just the Lewis acidity.