CIQSO-Center for Research in Sustainable Chemistry and, Department of Chemistry, University of Huelva, Campus de El Carmen s/n, 21071, Huelva, Spain.
Instituto Universitario Mixto de Tecnología Química (ITQ-UPV), Universitat Politècnica de València, Av. de los Naranjos s/n, 46022, Valencia, Spain.
Chemistry. 2020 Nov 6;26(62):14229-14235. doi: 10.1002/chem.202001893. Epub 2020 Sep 30.
The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy) (DMAP) ] complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy) (DMAP)] . The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst.
通过可见光照射 [Ru(bpy)(DMAP)] 配合物释放 4-N,N-二甲基氨基吡啶（DMAP）实现光控有机催化。选择苯甲醇和乙酸酐的乙酰化反应作为模型反应。预催化剂在波长大于 455nm 的光照射下释放一个 DMAP 分子。光化学反应通过稳态辐照和超快瞬态吸收光谱进行表征。后者能够观察到 MLCT 态和五配位中间物 [Ru(bpy)(DMAP)] 的光谱特征。释放的 DMAP 以高达 99%的化学产率催化各种苯甲醇的乙酰化反应。对照实验明确表明，释放的 DMAP 是催化剂的作用。
