Abstract
Comprehensive SummaryMechanistic studies of the palladium catalyst activation with halide additives are of great importance to palladium catalysis. In this work, XAFS spectroscopy and cyclic voltammetry were utilized to study real structures of Pd(OAc)2 in solution with different inorganic halogen additives. XAFS results demonstrate that Pd maintained +2 in the presence of excessive LiCl, LiBr, ZnCl2, ZnBr2, and NaI. Fitting results of EXAFS spectra revealed that the Pd's first shell is replaced by halogen partially or completely depending on the halogen species. DFT calculations were conducted to identify the most reliable solvated structures. The combined experimental and computational studies elucidate the critical role of inorganic halide additives in Pd chemistry.
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