α-Substituted Benzylic Complexes of Palladium(II) as Precursors of Palladium Hydrides

Abstract

The adoption of a pseudoallylic (η3) form makes palladium benzylic derivatives a class of stabilized palladium alkyls that can undergo β-H elimination reactions in a more controlled way. α-(Pentafluorophenylmethyl)benzyl palladium complexes have been studied, and they decompose by β-H elimination to give palladium hydrides that, depending on the auxiliary ligands, can: (a) transmetalate to another palladium atom and, by reductive elimination, give hydrogenated products; this process is favored for a combination of bridging ligands (i.e., halogens) and low coordinating ligands. (b) Be used as a hydride source and get trapped by a diene to give palladium allylic derivatives. The presence of carbon monoxide does not induce a β-H elimination reaction, and only CO insertion into the Pd–benzyl bond to give acyl derivatives is observed.