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An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization
https://oist.repo.nii.ac.jp/records/2576
https://oist.repo.nii.ac.jp/records/2576703bdf59-b96b-4fa3-96ae-c1c2102ac9c7
名前 / ファイル | ライセンス | アクション |
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jacs.1c12599(1) (5.1 MB)
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Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (https://creativecommons.org/licenses/by-nc-nd/4.0/)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2022-02-28 | |||||
タイトル | ||||||
言語 | en | |||||
タイトル | An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization | |||||
言語 | ||||||
言語 | eng | |||||
資源タイプ | ||||||
資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||
資源タイプ | journal article | |||||
著者(英) |
Xing, Liwen
× Xing, Liwen× Liu, Ji-Ren× Hong, Xin× Houk, Kendall N.× Luscombe, Christine K. |
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書誌情報 |
en : Journal of the American Chemical Society 巻 144, 号 5, p. 2311-2322, 発行日 2022-01-31 |
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抄録 | ||||||
内容記述タイプ | Other | |||||
内容記述 | The Carothers equation is often used to predict the utility of a small molecule reaction in a polymerization. In this study, we present the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization to synthesize a donor–acceptor (D–A) polymer of 3,3′-dihexyl-2,2′-bithiophene and 2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl, which go counter to the Carothers equation. It is uncovered that the second chain extension cross-coupling proceeds much more efficiently than the first cross-coupling and the homocoupling side reaction (at least 1 order of magnitude faster) leading to unexpectedly low homocoupling defects and high molecular weight polymers. Kinetic analyses show that C–H bond activation is rate-determining in the first cross-coupling but not in the second cross-coupling. Based on DFT calculations, the high cross-coupling rate in the second cross-coupling was ascribed to the strong Pd-thiophene interaction in the Pd-mediated C–H bond activation transition state, which decreases the energy barrier of the Pd-mediated C–H bond activation. These results have implications beyond polymerizations and can be used to ease the synthesis of a wide range of molecules where C–H bond activation may be the limiting factor. | |||||
出版者 | ||||||
出版者 | American Chemical Society | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 0002-7863 | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 1520-5126 | |||||
PubMed番号 | ||||||
関連タイプ | isIdenticalTo | |||||
識別子タイプ | PMID | |||||
関連識別子 | info:pmid/35100507 | |||||
DOI | ||||||
関連タイプ | isIdenticalTo | |||||
識別子タイプ | DOI | |||||
関連識別子 | info:doi/10.1021/jacs.1c12599 | |||||
権利 | ||||||
権利情報 | © 2022 The Authors. | |||||
権利 | ||||||
権利情報 | ACS AuthorChoice with CC-BY-NC-ND. | |||||
関連サイト | ||||||
識別子タイプ | URI | |||||
関連識別子 | https://pubs.acs.org/doi/10.1021/jacs.1c12599 | |||||
著者版フラグ | ||||||
出版タイプ | VoR | |||||
出版タイプResource | http://purl.org/coar/version/c_970fb48d4fbd8a85 |