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Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide

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Title: Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide
Authors: Hasegawa, Jun-ya Browse this author →KAKEN DB
Miyazaki, Ray Browse this author
Maeda, Chihiro Browse this author →KAKEN DB
Ema, Tadashi Browse this author →KAKEN DB
Keywords: carbon dioxide fixation
cyclic carbonates
DFT calculations
epoxides
porphyrinoids
Issue Date: Oct-2016
Publisher: Wiley-VCH
Journal Title: Chemical record
Volume: 16
Issue: 5
Start Page: 2260
End Page: 2267
Publisher DOI: 10.1002/tcr.201600053
PMID: 27308866
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.
Rights: ©2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ; This is the accepted version of the following article: http://dx.doi.org/10.1002/tcr.201600053, which has been published in final form at The Chemical record, Vol.16(5) October, 2016. This article may be used for non-commercial purposes in accordance with the Wiley Self-Archiving Policy [olabout.wiley.com/WileyCDA/Section/id-820227.html].
Type: article (author version)
URI: http://hdl.handle.net/2115/67235
Appears in Collections:触媒科学研究所 (Institute for Catalysis) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 長谷川 淳也

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