Computational and Experimental Studies of Methyl Group Exchange between Palladium(II) Centers

The disproportionation of 2 equiv of (L)(2)Pd-(CH3)(X) to form 1 equiv, of (L)(2)Pd(CH3)(2) and 1 equiv, of (L)(2)Pd(X)(2) could serve as a key step in the catalytic oxidative oligomerization of methane. The thermodynamics associated with this transformation have been evaluated as a function of the supporting ligands L and X using DFT calculations. With these calculations as a guide, we demonstrate the first experimental example of disproportionation of a Pd-II monomethyl complex to generate a Pd-II dimethyl species using (Bu-t-bpy)Pd(CH3)(CH2COCH3) Bu-t-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) as the starting material.