To in silico get new catalysts, molecular descriptors and visualization tools can represent a remarkable aid. First, we introduced a sterical index, called vBur that is able to give a quantitative value to the sterical hindrance that a N-heterocyclic carbene (NHC) ligand or phosphine produces to the metal center.<br/>Second, a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted the similarity between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.<br/>Third, by Density Functional Theory calculations, the examination of cross metathesis reactions leading to the most comprehensible product has been conducted to uncover computationally the origin of the chemo-, regio- and stereoselectivity. The comparison between the relative stabilities of all involved intermediates and products suggests the probability for the respective pathway. Additionally, the respective transition states for each reaction are the key to predicting the regio- and stereoselectivity because these species define the energy barriers needed to be overcome to form the new olefin as final product. The broad range of studied reactions allows for concluding in detail the points to pay attention and thus gives a general recipe to better understand the chemo-, regio- and stereoselectivity in new olefin metathesis reactions, by a web server.

How to predict reactivity on organometallic reactions from user-friendly computational tools

255th National Meeting (2018)

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