Preparation and catalytic properties of poly(methyl methacrylate)-supported Pd0 obtained from room-temperature, dark reduction of ionic aggregates of the unstable Pd2+ solution ionomer

Abstract

A poly(methyl methacrylate)-supported Pd⁰ nanocatalyst was successfully prepared from solution reaction of Pd(CH₃COO)₂ with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA–MAA). The reaction was carried out in a benzene/methanol mixed solvent in the dark at room temperature (∼25 °C) in the absence of a typical chemical reductant. There was coordination between the Pd⁰ nanoclusters and MMA–MAA, resulting in Pd⁰ nanoclusters being stably and uniformly dispersed in the MMA–MAA matrix, with an average particle size of ∼2.5 ± 0.5 nm. Mechanistically, it can tentatively be proposed that PMMA-ionomerization of the Pd²⁺ ions produces intramolecular –2COO⁻–Pd²⁺ aggregate cross-links in the solution. On swelling of the chain-segments that are covalently bound via multiple C–C bonds, the resultant elastic forces cause instantaneous dissociation at the O–Pd coordination bonds to give transient bare (i.e., uncoordinated), highly-oxidative Pd²⁺ ions and H⁺-associative carboxylate groups, both of which rapidly scavenge electrons and protons, respectively, of the active α-H atoms abstracted from the methanol molecules of the solvent to make Pd⁰ nanoclusters supported by the re-formed MMA–MAA. The MMA–MAA acid copolymer, without itself undergoing any permanent chemical change, serves as a mechanical activator or catalyst for the mechanochemical reduction of Pd(CH₃COO)₂ under mild conditions. Compared with traditional Pd/C catalysts, this Pd⁰ nanocatalyst exhibited more excellent catalytic efficiency and reusability in the Heck reaction between iodobenzene and styrene, and it could be easily separated. The supported Pd⁰ nanocatalyst prepared using this novel and simple preparation method may display high-efficiency catalytic properties for other cross coupling reactions.