Computational Studies of Functionalised [Pn₇] (Pn = P, As) Clusters for the Catalysed Hydroboration of Pyridine; Exploration of the Treatment of Entropy

Zintl clusters have recently emerged as competent catalysts for a variety of organic transformations. Herein, we report the mechanism of functionalised Zintl-cluster catalysed hydroboration of pyridine and subsequent analysis of the energetic profile of this catalytic cycle, employing the energetic span model to identify key states that underpin the catalytic activity, and observe how these states and other properties of the cycle change for several catalyst analogues. We also explore the effect of entropy, and how it is computed in solution, in determining the energetics and kinetics of the target systems.