Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide
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- Chihiro Maeda
- Division of Applied Chemistry Graduate School of Natural Science and Technology Okayama University Tsushima Okayama 700-8530 Japan
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- Junta Shimonishi
- Division of Applied Chemistry Graduate School of Natural Science and Technology Okayama University Tsushima Okayama 700-8530 Japan
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- Ray Miyazaki
- Catalysis Research Center Hokkaido University Kita 21, Nishi 10, Kita-ku Sapporo 001-0021 Japan
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- Jun‐ya Hasegawa
- Catalysis Research Center Hokkaido University Kita 21, Nishi 10, Kita-ku Sapporo 001-0021 Japan
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- Tadashi Ema
- Division of Applied Chemistry Graduate School of Natural Science and Technology Okayama University Tsushima Okayama 700-8530 Japan
書誌事項
- 公開日
- 2016-03-17
- 資源種別
- journal article
- 権利情報
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- http://onlinelibrary.wiley.com/termsAndConditions#vor
- DOI
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- 10.1002/chem.201600164
- 10.1002/chin.201639054
- 公開者
- Wiley
この論文をさがす
説明
<jats:title>Abstract</jats:title><jats:p>Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the <jats:italic>meta</jats:italic>, <jats:italic>para</jats:italic>, or <jats:italic>ortho</jats:italic> positions of <jats:italic>meso</jats:italic>‐phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent‐free conditions. The <jats:italic>meta</jats:italic>‐substituted catalysts exhibited high catalytic performance, whereas the <jats:italic>para</jats:italic>‐ and <jats:italic>ortho</jats:italic>‐substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the <jats:italic>meta</jats:italic>‐substituted catalyst, which could use the flexible quaternary ammonium cation at the <jats:italic>meta</jats:italic> position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the <jats:italic>meta</jats:italic> positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500 h<jats:sup>−1</jats:sup> at 170 °C) at an initial CO<jats:sub>2</jats:sub> pressure of 1.7 MPa; catalyzed the reaction even at atmospheric CO<jats:sub>2</jats:sub> pressure (balloon) at ambient temperature (20 °C); and was applicable to a broad range of substrates, including terminal and internal epoxides.</jats:p>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 22 (19), 6556-6563, 2016-03-17
Wiley