Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald-Hartwig Amination Reaction

Scaling relations are widely used to study surface reactions. However, the exploration of its utility in homogeneous catalysis is currently far less reported. In this work, we have investigated the transferability of the concept of scaling relations to a homogeneous catalysis reaction known as the Buchwald-Hartwig amination (BHA) reaction. The reaction of PhBr with MeNH2 using 37 different Pd-L complexes (L = phosphine ligand) is studied, and scaling relations are established among the reaction intermediates and transition states. Using the scaling relations, we construct volcano plots, which is the plot of the log(rate) vs the descriptor intermediate energy. The insights from the volcano plots agree well with the experimental trends from the literature and give direction toward better catalyst design.