Synthesis of Well-Defined High-Valent Palladium Complexes by Oxidation of Their Palladium(II) Precursors.

The last decade has witnessed the rapid development of high-valent Pd-involved organic transformations. This has also led to a steadily growing number of publications concerning the preparation of isolable and characterizable palladium(III) and palladium(IV) complexes. A variety of one-electron and two-electron oxidants have been employed to give access to high-oxidation-state Pd compounds. Undoubtedly, the study of these stoichiometric reactions has great implications for relevant Pd-mediated catalysis. In this minireview, the focus is on the synthetic approaches to structurally determined Pd complexes starting from their Pd precursors, and the advances in this research area from early 2010 to late 2019 will be highlighted. Chemical oxidations exploiting various oxidizing agents including 1) hypervalent iodine reagents; 2) halogens; 3) electrophilic fluorination reagents; 4) alkyl/aryl halides; 5) ferrocenium salts; 6) peroxides/O ; 7) sulfonyl chlorides; and 8) others are covered. A "greener" electrooxidation manner has also been reviewed.