Light- and Heat-Responsive Frustrated Lewis Pair Enables On-Demand Fixation of Ethylene

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-04-22 DOI:10.1021/jacs.5c03130

Taiki Yanagi, Jun Takaya

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引用次数: 0

Abstract

Frustrated Lewis pairs (FLPs) have been widely utilized as useful reagents and catalysts for activation of small molecules (SMs) through thermally controlled equilibrium formation of FLP–SM adducts. Herein, we report a light- and heat-responsive FLP system for on-demand fixation of ethylene. The system realizes capture and release of ethylene orthogonally triggered by visible light and heat, demonstrating potential utility as a nonmetallic and environmentally benign method for separation and storage of ethylene. The applicability to other alkenes is also demonstrated. Mechanistic investigations clarify that the photoexcited FLP enables stepwise radical addition to ethylene, followed by skeletal rearrangement to afford the FLP–ethylene adduct, which undergoes thermally promoted, concerted retro-cycloaddition to release ethylene and the free FLP. As a synthetic application, nonequilibrium, selective cis-to-trans isomerization of cyclooctene is achieved through the capture and release of cyclooctene with the FLP. This work discloses unique photochemical reactivity and application of FLPs, leading to further expansion of FLP chemistry into chemical science.

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光和热响应挫折刘易斯对实现按需固定乙烯

受挫刘易斯对（FLPs）已被广泛用作小分子（SMs）通过热控制平衡形成的FLP-SM加合物而活化的有用试剂和催化剂。在这里，我们报告了一个光和热响应FLP系统按需固定乙烯。该系统实现了由可见光和热正交触发的乙烯捕获和释放，展示了作为分离和储存乙烯的非金属和环保方法的潜在实用性。对其它烯烃的适用性也进行了论证。机理研究表明，光激发的FLP能够逐步自由基加成乙烯，随后骨架重排提供FLP -乙烯加合物，该加合物经过热促进，协同反环加成以释放乙烯和游离FLP。作为一种合成应用，环烯的非平衡、选择性顺式到反式异构化是通过FLP捕获和释放环烯实现的。本工作揭示了FLP独特的光化学反应性及其应用，使FLP化学进一步扩展到化学科学领域。

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.