A New ternary organometallic Pd(ii)/Fe(iii)/Ru(iii) self-assembly monolayer: the essential ensemble synergistic for improving catalytic activity

Abstract

The synergistic catalytic effect in a hetero-trimetallic catalytic monolayer is one of the intriguing topics because the additive effects of the second or third component play an important role in improving the activity. In this paper, a new Schiff-base organometallic nanosheet containing Pd/Fe/Ru immobilized on graphene oxide (GO@H-Pd/Fe/Ru) was prepared and characterized. The catalytic performance of GO@H-Pd/Fe/Ru and synergistic effect were systematically investigated. GO@H-Pd/Fe/Ru was found to be an efficient catalyst with higher turnover frequency (TOF) (26 892 h⁻¹) and stability with recyclability of at least 10 times in the Suzuki–Miyaura coupling reaction. The deactivation mechanism was caused by the aggregation of the active species, loss of the active species, the changes of the organometallic complex, and active sites covered by adsorbed elements during the catalytic process. GO@H-Pd/Fe/Ru was a heterogeneous catalyst, as confirmed by kinetic studies with in situ FT-IR, thermal filtration tests and poisoning tests. The real active center containing Pd, Ru and Fe arranged as Fe(III)–Ru(III)–Pd(II)–Fe(III) was proposed. Although Ru(III) and Fe(III) were shown to be less active or inactive, the addition of Fe and Ru could effectively improve the entire activity by their ‘‘indirect’’ function, in which Fe or Ru made Pd more negative and more stable. The ensemble synergistic effect between metals, the ligand and support was described as a process in which the electron was transferred from GO via ligand to Ru, and then to Pd or from Fe to Pd to make Pd more negative, promoting the oxidation addition with aryl halide. Also, the vicinity of Ru around Pd as the promoter adsorbed aryl boronic acid, which facilitates its synergism to react with the oxidation intermediate to the trans-metallic intermediate.