Deep Red to Near-Infrared Light-Controlled Ruthenium-Catalyzed Olefin Metathesis
Deep Red to Near-Infrared Light-Controlled Ruthenium-Catalyzed Olefin Metathesis
复制标题
DOI：
10.1021/acscatal.3c00473
复制
发表时间：
2023-04-07
期刊：
影响因子：
12.9
通讯作者：
Rovis, Tomislav
中科院分区：
文献类型：
--
作者：
Cabanero, David C.;Nguyen, Jennifer A.;Rovis, Tomislav
利用深红色至近红外光（600-800 nm）与锇（II）光催化剂（通过自旋禁止激发直接激发到三重态）结合，开发了一种激活潜在钌烯烃分解催化剂的系统。通过原位LED核磁共振动力学研究和循环伏安法研究，提出了潜在溶剂配位阳离子预催化剂的激发态单电子还原作为活化和光控制的操作机制。在光照射下发现了极好的时空控制水平。近红外烯烃复合反应表现出通过较短波长的光屏障的光穿透性提高，这是一种通过开环复合聚合来模制双环戊二烯的控制元件。
A system has been developed to activate a latent ruthenium olefin metathesis catalyst using deep red to near-infrared light (600-800 nm) in conjunction with an osmium(II) photocatalyst that is directly excited to its triplet state via spin-forbidden excitation. An excited-state single-electron reduction of a latent solvent-coordinated, cationic precatalyst is proposed as the operating mechanism for activation and photocontrol, as probed via in situ LED NMR kinetic studies and cyclic voltammetry. Excellent levels of spatiotemporal control are found under light irradiation. NIR olefin metathesis exhibits improved light penetration through barriers over shorter wavelengths of light, a control element that was deployed to mold dicyclopentadiene via ring-opening metathesis polymerization.