Further exploration of the physicochemical nature of μ2-bridge-relevant deprotonations via the elucidation of four kinds of alditol complexes
Date
2024-12-12
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Physical Chemistry Chemical Physics
Abstract
Single-crystal structures of four alditol complexes are presented. In LuCl3/galactitol and ScCl3/myo-inositol complexes, μ2-bridge-relevant deprotonations were observed. The polarization from two rare earth ions in the μ2-bridge activates the chemically inert OH and promotes deprotonation. Additionally, mass spectrometry, pH experiments, and quantum chemistry calculations were conducted to enhance our understanding of the μ2-bridge-relevant deprotonations. A common structural feature of the complexes where μ2-bridge-relevant deprotonation takes place is that two metal ions and two oxygen atoms in two μ2-bridges form an M2O2 cluster. The four atoms in the M2O2 cluster make up a parallelogram. Such a structure is useful to balance the strong coulombic repulsions between two M3+ and between two O−. In the ScCl3/myo-inositol complex, the deprotonation exhibits a characteristic of regional/chiral selectivity. Galactitol is a third alditol ligand where μ2-bridge-relevant deprotonation is observed. The flexible backbone of the galactitol allows the formation of more five-membered chelating rings and six-membered chelating rings, which are used to stabilize the rare earth ions of the μ2-bridge. The coordination makes the backbone of galactitol deviate from the zigzag conformation. The above results are helpful in the rational design of high-performance catalysts.
Description
This article was originally published in Physical Chemistry Chemical Physics. The version of record is available at: https://doi.org/10.1039/D4CP03612C.
This journal is © the Owner Societies 2025.
This article will be embargoed until 12/12/2025.
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Citation
Wu, Yi, Linchen Xie, Ye Jiang, Anqi He, Da Li, Limin Yang, Yizhuang Xu, Kexin Liu, Yukihiro Ozaki, and Isao Noda. “Further Exploration of the Physicochemical Nature of Μ2-Bridge-Relevant Deprotonations via the Elucidation of Four Kinds of Alditol Complexes.” Phys. Chem. Chem. Phys. 27, no. 3 (2025): 1503–14. https://doi.org/10.1039/D4CP03612C.