TY - JOUR
T1 - Bifunctional catalysts based on m-phenylene-bridged porphyrin dimer and trimer platforms
T2 - Synthesis of cyclic carbonates from carbon dioxide and epoxides
AU - Maeda, Chihiro
AU - Taniguchi, Tomoya
AU - Ogawa, Kanae
AU - Ema, Tadashi
N1 - Publisher Copyright:
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/1/2
Y1 - 2015/1/2
N2 - Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO2 with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220000 and 46000 h-1, respectively, for the magnesium catalyst, and 310000 and 40000 h-1, respectively, for the zinc catalyst. Results obtained with a zinc/free-base hybrid diporphyrin catalyst demonstrated that the Br- ions on the adjacent porphyrin moiety also function as nucleophiles.
AB - Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO2 with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220000 and 46000 h-1, respectively, for the magnesium catalyst, and 310000 and 40000 h-1, respectively, for the zinc catalyst. Results obtained with a zinc/free-base hybrid diporphyrin catalyst demonstrated that the Br- ions on the adjacent porphyrin moiety also function as nucleophiles.
KW - Carbon dioxide fixation
KW - Cyclic carbonates
KW - Homogeneous catalysis
KW - Porphyrinoids
KW - Zinc
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U2 - 10.1002/anie.201409729
DO - 10.1002/anie.201409729
M3 - Article
AN - SCOPUS:84920163168
VL - 54
SP - 134
EP - 138
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 1
ER -