Shining Fresh Light on Complex Photoredox Mechanisms through Isolation of Intermediate Radical Anions.
Shining Fresh Light on Complex Photoredox Mechanisms through Isolation of Intermediate Radical Anions.
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DOI：
10.1021/acscatal.3c02515
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发表时间：
2023-07-21
期刊：
影响因子：
12.9
通讯作者：
Scott, Daniel J.
中科院分区：
文献类型：
--
作者：
Horsewill, Samuel J.;Hierlmeier, Gabriele;Farasat, Zahra;Barham, Joshua P.;Scott, Daniel J.
近年来，光氧化还原催化（PRC）获得了巨大而广泛的兴趣，但也受到显着的机理不确定性，甚至有争议。为了提供一种方法，通过该方法可以开始填补缺失的理解，我们在本文中证明，可以分离代表性PRC催化剂（PC）的单电子还原产物作为真实材料。具体地，在穴状配体存在下，9，10-二氰基蒽和萘单酰胺衍生物的KC 8还原提供了方便地获得相应的[K（穴状配体）+][PC·-]盐作为清洁材料，其可以通过包括EPR和XRD的技术完全表征。由于PC·-态是PRC反应中的关键中间体，因此这种分离允许对这些阴离子的特定反应性及其机理作用进行高度受控的研究。作为这一原则的演示，我们表明，这些盐可以用来方便地询问最近，高调的“conPET”和“电子PRC”的反应，这是目前的主题都显着的兴趣和激烈的争议的机制。使用非常简单的实验，我们能够提供这些反应的潜在机制的惊人见解，并观察到令人惊讶的隐藏复杂性水平，否则将非常具有挑战性的识别，并强调询问和解释PRC机制时所需的护理和控制。这些研究为将来使用相同的PC·-隔离策略研究围绕conPET、e-PRC和其他PRC反应机制的更广泛问题提供了基础。
Photoredox catalysis (PRC) has gained enormous and wide-ranging interest in recent years but has also been subject to significant mechanistic uncertainty, even controversy. To provide a method by which the missing understanding can begin to be filled in, we demonstrate herein that it is possible to isolate as authentic materials the one-electron reduction products of representative PRC catalysts (PCs). Specifically, KC8 reduction of both 9,10-dicyanoanthracene and a naphthalene monoamide derivative in the presence of a cryptand provides convenient access to the corresponding [K(crypt)+][PC·–] salts as clean materials that can be fully characterized by techniques including EPR and XRD. Because PC·– states are key intermediates in PRC reactions, such isolation allows for highly controlled study of these anions’ specific reactivity and hence their mechanistic roles. As a demonstration of this principle, we show that these salts can be used to conveniently interrogate the mechanisms of recent, high-profile “conPET” and “e-PRC” reactions, which are currently the subject of both significant interest and acute controversy. Using very simple experiments, we are able to provide striking insights into these reactions’ underlying mechanisms and to observe surprising levels of hidden complexity that would otherwise have been very challenging to identify and that emphasize the care and control that are needed when interrogating and interpreting PRC mechanisms. These studies provide a foundation for the study of a far broader range of questions around conPET, e-PRC, and other PRC reaction mechanisms in the future, using the same strategy of PC·– isolation.
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影响因子：
16.6
作者：
Coles, Max S.;Quach, Gina;Moore, Evan G.
通讯作者：
Moore, Evan G.
影响因子：
3.6
作者：
BARANY, G;SCHROLL, AL;HALSRUD, DA
通讯作者：
HALSRUD, DA
影响因子：
15
作者：
Cole JP;Chen DF;Kudisch M;Pearson RM;Lim CH;Miyake GM
通讯作者：
Miyake GM
影响因子：
15
作者：
Cowper NGW;Chernowsky CP;Williams OP;Wickens ZK
通讯作者：
Wickens ZK
DOI：
10.3891/acta.chem.scand.37b-0459
发表时间：
1983-01-01
期刊：
ACTA CHEMICA SCANDINAVICA SERIES B-ORGANIC CHEMISTRY AND BIOCHEMISTRY
影响因子：
--
作者：
ERIKSEN, J;LUND, H;NYVAD, AI
通讯作者：
NYVAD, AI