The behavior of palladium acetate is reviewed with respect to its synthesis, characterization, structure (in both solution and solid state), and activation pathways. In addition, comparisons of catalytic activities between pure palladium acetate and two common byproducts, Pd3 (OAc)5 (NO2 ) and polymeric [Pd(OAc)2 ]n , typically present in commercially available material are reviewed. Hence, this minireview serves as a concise guide for the users of palladium acetate from both academia and industry.
Commercially available palladium acetate often contains two major impurities, whose presence can impact the overall catalytic efficacy. This systematic study provides a comparison of the differences in catalytic activity of pure palladium acetate, Pd3(OAc)6, with the two impurities: Pd3(OAc)5(NO2) and polymeric [Pd(OAc)2]n in a variety of cross-coupling reactions. The solid state (13)C NMR spectra of all three compounds in conjunction with DFT calculations confirm their reported geometries.
A very convenient general method was developed for making tunable polypropylene-supported Pd complexes of electron-rich and bulky monodentate ligands such as Q-Phos, t-Bu3P, (Me2NC6H4)P(t-Bu)2 (Ata-Phos), and IPr-carbene as well as bidentate ligands such as BINAP, dppf, and dippf in 4−8% Pd loading. These catalysts have been utilized for Suzuki coupling of aryl chlorides and bromides with product conversions up to 100%. Minimal metal leaching has been observed in many cases. Many of these catalysts were recycled a few times in model systems with an undetected amount of Pd leaching.
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