%VBur index and steric maps: from predictive catalysis to machine learning

Abstract

Steric indices are parameters used in chemistry to describe the spatial arrangement of atoms or groups of atoms in molecules. They are important in determining the reactivity, stability, and physical properties of chemical compounds. One commonly used steric index is the steric hindrance, which refers to the obstruction or hindrance of movement in a molecule caused by bulky substituents or functional groups. Steric hindrance can affect the reactivity of a molecule by altering the accessibility of its reactive sites and influencing the geometry of its transition states. Notably, the Tolman cone angle and %V_Bur are prominent among these indices. Actually, steric effects can also be described using the concept of steric bulk, which refers to the space occupied by a molecule or functional group. Steric bulk can affect the solubility, melting point, boiling point, and viscosity of a substance. Even though electronic indices are more widely used, they have certain drawbacks that might shift preferences towards others. They present a higher computational cost, and often, the weight of electronics in correlation with chemical properties, e.g. binding energies, falls short in comparison to %V_Bur. However, it is worth noting that this may be because the steric index inherently captures part of the electronic content. Overall, steric indices play an important role in understanding the behaviour of chemical compounds and can be used to predict their reactivity, stability, and physical properties. Predictive chemistry is an approach to chemical research that uses computational methods to anticipate the properties and behaviour of these compounds and reactions, facilitating the design of new compounds and reactivities. Within this domain, predictive catalysis specifically targets the prediction of the performance and behaviour of catalysts. Ultimately, the goal is to identify new catalysts with optimal properties, leading to chemical processes that are both more efficient and sustainable. In this framework, %V_Bur can be a key metric for deepening our understanding of catalysis, emphasizing predictive catalysis and sustainability. Those latter concepts are needed to direct our efforts toward identifying the optimal catalyst for any reaction, minimizing waste, and reducing experimental efforts while maximizing the efficacy of the computational methods.