Immobilized Palladium Nanoparticles on Zirconium Carboxy-Aminophosphonates Nanosheets as an Efficient Recoverable Heterogeneous Catalyst for Suzuki–Miyaura and Heck Coupling

Zirconium phosphate glycine diphosphonate nanosheets (ZPGly) have been used as support for the preparation of solid palladium nanoparticles, namely Pd@ZPGly. Thanks to the presence of carboxy-aminophosponate groups on the layer surface, ZPGly-based materials were able to stabilize a high amount of palladium (up to 22 wt %) also minimizing the amount of metal leached in the final products of representative important cross-coupling processes selected for proving the catalysts’ efficiency. The catalytic systems have been fully characterized and used in low amounts (0.1 mol %) in the Suzuki–Miyaura and Heck cross-couplings. Moreover, the protocols were optimized for the use of recoverable azeotropic mixtures (aq. EtOH 96% or aq. CH3CN 84%, respectively) and in the flow procedure allowing one to isolate the final pure products, without any purification step, with very low residual palladium content and with a very low waste production.