We report a series of arylpalladium complexes of acetamidate, sulfonamidate, and deprotonated
oxazolidinone ligands that undergo reductive elimination with rates and yields that depend on the binding mode of the ancillary and amidate
ligands. Complexes of the acetamidate
ligands containing the bidentate
phosphines DPPF and
Xantphos as ancillary
ligands undergo reductive elimination. The rate and yield were higher from the complex ligated by
Xantphos, which contains a larger
bite angle. In contrast, the analogous amidate complex containing a single sterically hindered monodentate
ligand and a kappa2-bound amidate
ligand does not undergo reductive elimination. This trend of faster reductive elimination from complexes containing bidentate ancillary
ligands than from a complex with a single monodentate ancillary
ligand is unusual and is consistent with an effect of the denticity of the ancillary
ligand on the binding mode of the amidate. Complexes of sulfonamidate
ligands underwent reductive elimination faster than complexes of acetamidates, and reductive elimination occurred from complexes containing both bidentate and monodentate ancillary
ligands. Like reductive elimination from the acetamidate complexes, reductive eliminations from the sulfonamidate complexes were faster when the complexes possessed bidentate
Xantphos and kappa1-sulfonamidate
ligands.