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Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide.
Chem Rec. 2016 10; 16(5):2260-2267.CR

Abstract

Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

Authors+Show Affiliations

Institute for Catalysis, Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan. hasegawa@cat.hokudai.ac.jp.Institute for Catalysis, Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan.Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama 700-8530, Japan. cmaeda@okayama-u.ac.jp.Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama 700-8530, Japan. ema@cc.okayama-u.ac.jp.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

27308866

Citation

Hasegawa, Jun-Ya, et al. "Theoretical Study On Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides With Carbon Dioxide." Chemical Record (New York, N.Y.), vol. 16, no. 5, 2016, pp. 2260-2267.
Hasegawa JY, Miyazaki R, Maeda C, et al. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide. Chem Rec. 2016;16(5):2260-2267.
Hasegawa, J. Y., Miyazaki, R., Maeda, C., & Ema, T. (2016). Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide. Chemical Record (New York, N.Y.), 16(5), 2260-2267. https://doi.org/10.1002/tcr.201600053
Hasegawa JY, et al. Theoretical Study On Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides With Carbon Dioxide. Chem Rec. 2016;16(5):2260-2267. PubMed PMID: 27308866.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide. AU - Hasegawa,Jun-Ya, AU - Miyazaki,Ray, AU - Maeda,Chihiro, AU - Ema,Tadashi, Y1 - 2016/06/16/ PY - 2016/03/24/received PY - 2016/10/19/pubmed PY - 2016/10/19/medline PY - 2016/6/17/entrez KW - DFT calculations KW - carbon dioxide fixation KW - cyclic carbonates KW - epoxides KW - porphyrinoids SP - 2260 EP - 2267 JF - Chemical record (New York, N.Y.) JO - Chem Rec VL - 16 IS - 5 N2 - Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts. SN - 1528-0691 UR - https://www.unboundmedicine.com/medline/citation/27308866/Theoretical_Study_on_Highly_Active_Bifunctional_Metalloporphyrin_Catalysts_for_the_Coupling_Reaction_of_Epoxides_with_Carbon_Dioxide_ L2 - https://doi.org/10.1002/tcr.201600053 DB - PRIME DP - Unbound Medicine ER -
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