Carbon(sp3)-nitrogen bond-forming reductive elimination from phosphine-ligated alkylpalladium(II) amide complexes: A DFT study

DFT methods were employed to investigate C(sp³)-N bond-formation via reductive elimination from alkylpalladium(II) amide complexes. The hemi-lability of an ortho-methoxy substituent is computed to have minimal impact on reductive elimination barriers. In general, for both anilide and phosphine substituents, their steric impact is more substantial than electronic/Hammett factors. β-Hydrogen elimination is competitive with reductive elimination while β-methyl elimination is much less favorable. For phosphine-ligated Pd(II) amide complexes, the solvent impact on reductive elimination free energy barriers is small, and overall the substituent effects on either the phosphine or anilide ligand are subtle.