What Makes for a Bad Catalytic Cycle? A Theoretical Study on the Suzuki-Miyaura Reaction within the Energetic Span Model

The Suzuki-Miyaura cross-coupling reaction using PMe3, PPh3, and PtBu3 as ligands was studied theoretically with accurate density functional theory (DFT) methods and the Energetic Span Model. The energetic span model is a tool to compute catalytic turnover frequencies (TOF) from computationally obtained energy states. In this work the model is expanded to include turnover numbers (TON) and off-cycle intermediates. The results show that although the monophosphine route is the fastest pathway, the diphosphine cis route (accessible for small ligands) may also be reactive. The death sentence of the PMe3 catalyst is the possibility to reach the low energy trans diphosphine species, which substantially reduces the TON. In the PPh3 case, the formation of (PdL3)-L-0 was found to be the major drawback for efficient catalysis. The PtBu3 system is the most efficient of the three, as only the monophosphine mechanism is accessible.