Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide

Chihiro Maeda, Junta Shimonishi, Ray Miyazaki, Jun ya Hasegawa, Tadashi Ema

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84 Citations (Scopus)

Abstract

Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240000 at 120°C, turnover frequency (TOF)=31500h-1 at 170°C) at an initial CO2 pressure of 1.7MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20°C); and was applicable to a broad range of substrates, including terminal and internal epoxides.

Original languageEnglish
JournalChemistry - A European Journal
DOIs
Publication statusAccepted/In press - 2016

Fingerprint

Metalloporphyrins
Carbonates
Epoxy Compounds
Carbon Dioxide
Carbon dioxide
Nucleophiles
Catalysts
Balloons
Porphyrins
Ammonium Compounds
Discrete Fourier transforms
Catalysis
Atmospheric pressure
Cations
Zinc
Catalyst activity
Positive ions
Substrates
Temperature

Keywords

  • Carbon dioxide fixation
  • Cyclic carbonates
  • Epoxides
  • Homogeneous catalysts
  • Porphyrinoids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide",
abstract = "Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240000 at 120°C, turnover frequency (TOF)=31500h-1 at 170°C) at an initial CO2 pressure of 1.7MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20°C); and was applicable to a broad range of substrates, including terminal and internal epoxides.",
keywords = "Carbon dioxide fixation, Cyclic carbonates, Epoxides, Homogeneous catalysts, Porphyrinoids",
author = "Chihiro Maeda and Junta Shimonishi and Ray Miyazaki and Hasegawa, {Jun ya} and Tadashi Ema",
year = "2016",
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T1 - Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide

AU - Maeda, Chihiro

AU - Shimonishi, Junta

AU - Miyazaki, Ray

AU - Hasegawa, Jun ya

AU - Ema, Tadashi

PY - 2016

Y1 - 2016

N2 - Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240000 at 120°C, turnover frequency (TOF)=31500h-1 at 170°C) at an initial CO2 pressure of 1.7MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20°C); and was applicable to a broad range of substrates, including terminal and internal epoxides.

AB - Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240000 at 120°C, turnover frequency (TOF)=31500h-1 at 170°C) at an initial CO2 pressure of 1.7MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20°C); and was applicable to a broad range of substrates, including terminal and internal epoxides.

KW - Carbon dioxide fixation

KW - Cyclic carbonates

KW - Epoxides

KW - Homogeneous catalysts

KW - Porphyrinoids

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