Computational Studies on an Aminomethylation Precursor: (Xantphos)Pd(CH2NBn2)+

(Xantphos)­Pd­(CH2NBn2)+ is an important precursor for aminomethylation reactions. In this study, density functional theory is used to clarify the structure of the complex and the mechanism of these types of reactions. The complex can be described as a mixture of square-planar nitrogen-coordinated aminomethyl–Pd­(II) and triangular iminium-coordinated Pd(0). Frontier molecular orbital analysis favors the latter. The mechanisms of selected aminomethylation reactions are investigated by density functional theory calculations. The computational results reveal that the Xantphos ligand aids in forming iminium-coordinated palladium complexes, promotes the reductive elimination step of aminomethylation, and can stabilize Pd(0) species.