Green‐Light‐Driven Reductive Elimination of Chlorine from a Carbene‐Xanthylium Gold(III) Complex
Green‐Light‐Driven Reductive Elimination of Chlorine from a Carbene‐Xanthylium Gold(III) Complex
复制标题
绿色 — 光 — 驱动还原消除卡宾 — 苍耳金 (III) 络合物中的氯
DOI：
10.1002/anie.202206265
复制
发表时间：
2022
期刊：
影响因子：
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通讯作者：
Gabbaï, François P.
中科院分区：
文献类型：
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作者：
Park, Gyeongjin;Karimi, Mohammadjavad;Liu, Wei‐Chun;Gabbaï, François P.
随着支持清洁光还原卤素消除的后过渡金属平台的发现，我们现在描述了在 4 位被呫吨单元修饰的吲唑-3-亚基三氯化金络合物 ([7]+)。这种橙色络合物在光谱的可见部分具有低能带，归因于吲唑-3-亚基/呫吨鎓供体/受体二元体的电荷转移激发。在存在氯阱的情况下，对该配合物进行绿光照射，可彻底光消除氯自由基，产生相应的金 (I) 配合物。这种可见光诱导的光还原非常有效，量子产率接近 10%。 [7]+ 的中性类似物具有蒽基而不是苍基单元，被证明具有完全的光稳定性，这支持了 [7]+ 中存在的基于苍基的光氧化还原单元的重要性。
With the discovery of late transition metal platforms that support clean photoreductive halogen eliminations, we now describe an indazol‐3‐ylidene gold trichloride complex ([7]+) decorated at the 4‐position by a xanthylium unit. This orange complex features a low energy band in the visible part of the spectrum, assigned to the charge transfer excitation of the indazol‐3‐ylidene/xanthylium donor/acceptor dyad. Green‐light irradiation of this complex in the presence of a chlorine trap elicits the clean photoelimination of chlorine radicals, producing the corresponding gold(I) complex. This visible‐light‐induced photoreduction is very efficient, reaching quantum yields close to 10 %. A neutral analog of [7]+featuring an anthryl group rather than a xanthylium unit proved to be perfectly photostable, supporting the importance of the xanthylium‐based photoredox unit present in [7]+.