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Structural Design for Molecular Catalysts
Published in Qingmin Ji, Harald Fuchs, Soft Matters for Catalysts, 2019
Qingmin Ji, Qin Tang, Jonathan P. Hill, Katsuhiko Ariga
Metal complexes with phosphorous-type ligands have been employed in various transition metal–catalyzed organic reactions. It has been found that the electron-withdrawing groups of phosphinites increase the strength of the metal phosphorous bond and act as a better acceptor. Phosphinite complexes with different metals (for example Rh, Pd, etc.) have shown high catalytic activity in different homogenous or heterogeneous reactions. Farjadian and coworkers modified mesoporous silica with a series of mono-, di-, and tri-phosphinite ligands for the preparation of supported Pd phosphinite complexes [265]. High efficiency and stability of Pd catalysts in the phosphinite-functionalized silica supports were shown in the Heck coupling reaction. The high yields of the resulting products indicated the good reactivity of diverse (electron-neutral, -rich, and -poor) haloarenes in these heterogeneous systems. Through simple filtration, the catalyst can also be recycled for repeated usage.
Ketone transfer hydrogenation reactions catalyzed by catalysts based on a phosphinite ligand
Published in Journal of Coordination Chemistry, 2022
Duygu Elma Karakaş, Khadichakhan Rafikova, Akin Baysal, Nermin Meriç, Alexey Zazybin, Cezmi Kayan, Uğur Işik, Islam Sholpan Saparbaykyzy, Feyyaz Durap, Murat Aydemir
Transition metal complexes of phosphinite ligands exhibit good catalytic activity and structural alterability [23, 43–45], which led us to design new catalysts with new phosphinite ligands [25, 46–48]. We prefer arene ligands [49] because we know that (i) in an octahedral structure, ligands that act as the spectator automatically fill three adjacent coordination sites of ruthenium, while three facial sites are left for other functions, (ii) arene ligands which are relatively weak electron donors may be distinctively reactive on the metallic center, and (iii) the substitution pattern on the ring is flexible.