From the grafting of NHC-based Pd(II) complexes onto TiO2 to the in situ generation of Mott-Schottky heterojunctions: The boosting effect in the Suzuki-Miyaura reaction. Do the evolved Pd NPs act as reservoirs?

The assumption that the real active species involved in the Suzuki-Miyaura reaction are homogeneous, heterogeneous or both is often proposed. However a lack of characterization of the true catalytic entities and their monitoring makes assumptions somewhat elusive. Here, with the aim of getting new insights into the formation of active species in the Suzuki-Miyaura reaction, a family of palladium(II) complexes bearing bis(NHC) ligands was synthesized for immobilization at the surface of TiO2. The studies reveal that once the complexes are anchored onto TiO2, the mechanism governing the catalytic reaction is different from that observed for the non-anchored complexes. All complexes evolved to Pd NPs at the surface of TiO2 under reaction conditions and released Pd species in the liquid phase. Also, this reactivity was boosted by the in situ generation of Mott-Schottky heterojunctions, opening new routes towards the design of heterogenized catalysts for their further implementation in reverse-flow reactors. (C) 2021 Elsevier Inc. All rights reserved.

Automated summary

The study on a series of palladium(II) complexes with bis(NHC) ligands immobilized on TiO2 surface reveals that these complexes evolve to Pd NPs at the TiO2 surface under reaction conditions, releasing Pd species in the liquid phase. The reactivity is enhanced by the in situ generation of Mott-Schottky heterojunctions, leading to new pathways for the design of heterogenized catalysts in reverse-flow reactors.