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 language | English |
|---|---|
| Journal | Chemistry - A European Journal |
| DOIs | |
| Publication status | Accepted/In press - 2016 |
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Keywords
- Carbon dioxide fixation
- Cyclic carbonates
- Epoxides
- Homogeneous catalysts
- Porphyrinoids
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Highly Active and Robust Metalloporphyrin Catalysts for the Synthesis of Cyclic Carbonates from a Broad Range of Epoxides and Carbon Dioxide. / Maeda, Chihiro; Shimonishi, Junta; Miyazaki, Ray; Hasegawa, Jun ya; Ema, Tadashi.
In: Chemistry - A European Journal, 2016.Research output: Contribution to journal › Article
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TY - JOUR
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
UR - http://www.scopus.com/inward/record.url?scp=84961285194&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84961285194&partnerID=8YFLogxK
U2 - 10.1002/chem.201600164
DO - 10.1002/chem.201600164
M3 - Article
AN - SCOPUS:84961285194
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
ER -