1085512-00-0Relevant articles and documents
[Fe(bpy)3]2+-based porous organic polymers with boosted photocatalytic activity for recyclable organic transformations
Liu, Hong-Kun,Lei, Yi-Fei,Tian, Peng-Ju,Wang, Hui,Zhao, Xin,Li, Zhan-Ting,Zhang, Dan-Wei
, p. 6361 - 6367 (2021)
Three rigid metal porous organic polymers (POPs) based on an iron(ii) complex are prepared from the condensation reactions of an octahedral [Fe(bpy)3]2+-cored hexaaldehyde and three rod-like aromatic diamines. The POPs have been studied as the first series of earth-abundant metal complex-connected photocatalysts for heterogeneous visible light-driven oxidation of benzyl halides and enantioselective α-alkylation of aldehydes. Both yields and enantioselectivities of the reactions catalyzed by one of the POPs, which possesses the largest porosity, rival or even surpass those of the reactions homogeneously catalyzed by control [Fe(bpy)3]2+complexes. Moreover, POP catalysts are highly stable and exhibit a considerable activity after recycling 10 times.
A Bifunctional Photoaminocatalyst for the Alkylation of Aldehydes: Design, Analysis, and Mechanistic Studies
Rigotti, Thomas,Casado-Sánchez, Antonio,Cabrera, Silvia,Pérez-Ruiz, Raúl,Liras, Marta,De La Pe?a O'Shea, Víctor A.,Alemán, José
, p. 5928 - 5940 (2018)
A bifunctional photoaminocatalyst based on imidazolidinone and thioxanthone is presented. The preparation of these catalysts proceeds in a two-step synthesis that allows an easy tuning of the steric properties. The photophysical and electrochemical data of the imidazolidinone photocatalysts have been determined, indicating that the catalysts can work under visible light conditions. To corroborate the experimental observations, ground state geometry optimization and energy transition studies of thioxanthone and bifunctional catalyst 4c were optimized by time-dependent density functional theory (TD DFT) calculations. The alkylation of aldehydes with this photoaminocatalyst works with high enantioselectivities and yields due to the stereoelectronic properties of the catalyst. A rational mechanistic cycle based on different mechanistic experiments, TD DFT calculations, and laser flash photolysis is presented.
Aluminum(III) Salen Complexes as Active Photoredox Catalysts
Gualandi, Andrea,Marchini, Marianna,Mengozzi, Luca,Kidanu, Hagos Tesfay,Franc, Antoine,Ceroni, Paola,Cozzi, Pier Giorgio
, p. 1486 - 1490 (2020)
Metallosalen are privileged complexes that have found important applications in catalysis. In addition, their luminescent properties have also been studied and used for sensing and biological applications. Salen metal complexes can be efficient photosensitizers, but they can also participate to electron transfer processes. Indeed, we have found that commercially available [Al(Salen)Cl] is an efficient photoredox catalyst for the synergistic stereoselective reaction of alkyl aldehydes with different bromo ketones and malonates to give the corresponding enantioenriched α-alkylated derivatives. The reaction was performed in the presence of a MacMillan catalyst. [Al(Salen)Cl] is able to replace ruthenium complexes, showing that also aluminum complexes can be used in promoting photoredox catalytic reactions.
8-Mercaptoquinoline as a Ligand for Enhancing the Photocatalytic Activity of Pt(II) Coordination Complexes: Reactions and Mechanistic Insights
Casado-Sánchez, Antonio,Uygur, Mustafa,González-Mu?oz, Daniel,Aguilar-Galindo, Fernando,Nova-Fernández, José Luis,Arranz-Plaza, Judith,Díaz-Tendero, Sergio,Cabrera, Silvia,Manche?o, Olga García,Alemán, José
, p. 6437 - 6447 (2019/05/24)
A family of quinoline-platinum(II) complexes as efficient photocatalysts is presented. Their key characteristic is their easy preparation by coordination of the readily available 8-hydroxy- or 8-thio-quinoline ligands, which are well known for their strong chelating ability to different metal ions. In the different photochemical transformations investigated, such as cross-dehydrogenative coupling, oxidation of arylboronic acids, and asymmetric alkylation of aldehydes, 8-mercaptoquinoline-Pt(II) complex proved to be the most general catalyst. Moreover, quenching experiments showed that, contrary to related methods reported in the literature, these complexes followed an oxidative quenching mechanism in all transformations studied. Besides, simulations performed with high-level ab initio methods of the complexes have helped to understand their photocatalytic activity.
