Deep Red to Near-Infrared Light-Controlled Ruthenium-Catalyzed Olefin Metathesis

被引：24

作者：

Cabanero, David C. ^{[1
]}

Nguyen, Jennifer A. ^{[1
]}

Cazin, Catherine S. J. ^{[2
,3
]}

Nolan, Steven P. ^{[2
,3
]}

Rovis, Tomislav ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

[2] Univ Ghent, Dept Chem, B-9000 Ghent, Belgium

[3] Univ Ghent, Ctr Sustainable Chem, B-9000 Ghent, Belgium

来源：

ACS CATALYSIS | 2023年 / 13卷 / 07期

基金：

美国国家科学基金会;

关键词：

catalysts; photocatalysis; light; irradiation; metathesis; POLYMERIZATION; DECOMPOSITION; COMPLEXES;

D O I：

10.1021/acscatal.3c00473

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

收藏

页码：4384 / 4390

页数：7

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