Bimetallic Substituted Ceria: An Alternative Approach to Ligand-Free Heck-Mizoroki Cross-Coupling Reactions

Abstract

This work describes Ce0.89Zr0.03Pd0.08O2-δ as a heterogeneous catalyst for Heck-Mizoroki reactions. The material was synthesised by urea-assisted solution combustion to give a zirconium-stabilised cerium fluorite structure, with a fraction of palladium incorporated into the host structure. Characterisation techniques included ICP-OES, P-XRD and electron microscopy. The catalyst illustrated a high TOF of 1860 h−1 for the cross-coupling of iodobenzene with methyl acrylate, when trimethylamine (TEA) was used as a base and dimethylformamide (DMF) as the solvent at 130 °C. To establish the activity of coupling pairs, screening was limited to aryliodobenzenes, with various electronic properties, to determine the influence of aryliodobenzene electronic density on the trans product yield. Electron-donating substituents showed good yields, while electron-withdrawing groups had lower yields. Furthermore, various classes of electron-deficient olefins were screened to determine any effect on the trans product yield. Electron-deficient olefins showed higher yields with regard to the trans product than neutral styrene.