Pyrazolin-5-ylidene palladium(II) complexes: Synthesis, characterization, and application in the direct arylation of pentafluorobenzene

Abstract

Ten palladium(II) complexes bearing a pyrazolin-5-ylidene ligand have been synthesized by oxidative addition and silver carbene transfer pathways. The weakly bound acetonitrile ligand in the initially obtained trans-[PdBr 2(MeCN)(Pyry)] complex (6, Pyry = 1-phenyl-2,3-dimethylpyrazolin-5- ylidene) could be replaced by other donor ligands, and additional NHC ligands were introduced either by silver carbene transfer reactions or via reaction with in situ generated free carbenes. Using our previously reported 13C NMR-based electronic parameter, the pyrazolin-5-ylidene ligand is estimated to be among the most strongly donating ligands on our scale so far. The complexes obtained were employed as catalysts for the direct arylation of pentafluorobenzene with moderate to good yields under optimized conditions. © 2012 American Chemical Society.