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Slow Reactant–Water Exchange and High Catalytic Performance of Water‐Tolerant Lewis Acids |
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| Authors: | Yusuke Koito Dr. Kiyotaka Nakajima Prof. Hisayoshi Kobayashi Ryota Hasegawa Dr. Masaaki Kitano Prof. Michikazu Hara |
| Affiliation: | 1. Materials and Structures Laboratory, Tokyo Institute of Technology, Nagatsuta, Midori‐ku Yokohama 226‐8503 (Japan);2. Research Fellow of Japan Society for the Promotion of Science (JSPS), 5‐3‐1 Chiyoda‐ku, Tokyo 102‐0083 (Japan);3. Japan Science and Technology (JST) Agency, PRESTO, 4‐1‐8 Honcho, Kawaguchi 332‐0012 (Japan);4. Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo‐ku, Kyoto 606‐8585 (Japan);5. Materials Research Center for Element Strategy, Tokyo Institute of Technology, Nagatsuta, Midori‐ku, Yokohama 226‐8503 (Japan);6. Japan Science and Technology (JST) Agency, ALCA, 4‐1‐8 Honcho, Kawaguchi 332‐0012 (Japan) |
| Abstract: | 31P nuclear magnetic resonance (NMR) spectroscopic measurement with trimethylphosphine oxide (TMPO) was applied to evaluate the Lewis acid catalysis of various metal triflates in water. The original 31P NMR chemical shift and line width of TMPO is changed by the direct interaction of TMPO molecules with the Lewis acid sites of metal triflates. [Sc(OTf)3] and [In(OTf)3] had larger changes in 31P chemical shift and line width by formation of the Lewis acid–TMPO complex than other metal triflates. It originates from the strong interaction between the Lewis acid and TMPO, which results in higher stability of [Sc(OTf)3TMPO] and [In(OTf)3TMPO] complexes than other metal triflate–TMPO complexes. The catalytic activities of [Sc(OTf)3] and [In(OTf)3] for Lewis acid‐catalyzed reactions with carbonyl compounds in water were far superior to the other metal triflates, which indicates that the high stability of metal triflate–carbonyl compound complexes cause high catalytic performance for these reactions. Density functional theory (DFT) calculation suggests that low LUMO levels of [Sc(OTf)3] and [In(OTf)3] would be responsible for the formation of stable coordination intermediate with nucleophilic reactant in water. |
| Keywords: | carbonyl compounds density functional calculations Lewis acids metal triflates NMR spectroscopy |