Aryl dechlorination and defluorination with an organic super-photoreductant.,Photochemical & Photobiological Sciences

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Aryl dechlorination and defluorination with an organic super-photoreductant.
Photochemical & Photobiological Sciences ( IF 2.7 ) Pub Date : 2020-06-26 , DOI: 10.1039/d0pp00127a
Felix Glaser ₁ , Christopher B Larsen ₁ , Christoph Kerzig ₁ , Oliver S Wenger ₁

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Direct excitation of the commercially available super-electron donor tetrakis(dimethylamino)ethylene (TDAE) with light-emitting diodes at 440 or 390 nm provides a stoichiometric reductant that is able to reduce aryl chlorides and fluorides. The method is very simple and requires only TDAE, substrate, and solvent at room temperature. The photoactive excited state of TDAE has a lifetime of 17.3 ns in cyclohexane at room temperature and an oxidation potential of ca. −3.4 V vs. SCE. This makes TDAE one of the strongest photoreductants able to operate on the basis of single excitation with visible photons. Direct substrate activation occurs in benzene, but acetone is reduced by photoexcited TDAE and substrate reduction takes place by a previously unexplored solvent radical anion mechanism. Our work shows that solvent can have a leveling effect on the photochemically available redox power, reminiscent of the pH-leveling effect that solvent has in acid–base chemistry.

中文翻译：

芳基脱氯和有机超光还原剂的脱氟。

用发光二极管在440或390 nm处直接激发市售的超电子供体四（二甲基氨基）乙烯（TDAE），可提供能够还原芳基氯化物和氟化物的化学计量的还原剂。该方法非常简单，在室温下仅需要TDAE，底物和溶剂。TDAE的光活化态在室温下在环己烷中的寿命为17.3 ns，氧化电势为。-3.4 V VS。SCE。这使TDAE成为最强的光还原剂之一，能够在可见光子的单激发下运行。直接的底物活化发生在苯中，但是丙酮被光激发的TDAE还原，而底物的还原则通过以前未开发的溶剂自由基阴离子机理进行。我们的工作表明，溶剂可以对光化学上可用的氧化还原能力产生流平作用，让人联想到溶剂在酸碱化学中具有的pH流平作用。

更新日期：2020-08-12

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