Scope and Challenge of Computational Methods for Studying Mechanism and Reactivity in Homogeneous Catalysis

Abstract

Computational methods based on quantum mechanical modelling are increasingly used to provide insight into mechanistic aspects of homogeneous catalysis. While the potential and value of such methods is obvious, it is also clear that it remains challenging to obtain reliable and predictive mechanistic insights from modelling. In this perspective, we assess the various factors influencing the quality of computational studies. While the type of electronic structure theory methodology used is of course of great importance, we argue that many other aspects can play a large role also. The other factors emphasized here include the treatment of entropic effects, solvation, the choice of the structural model, conformational complexity, the translation of computed relative Gibbs energies into a kinetic model, and the high demands required for the prediction of selectivity.

Machine learning dihydrogen activation in the chemical space surrounding Vaska's complex

“…Computational chemistry has become a powerful tool in homogeneous catalysis, and combined with experiments, delivers molecular models enabling the rational design of catalytic systems. [13][14][15][16][17][18][19][20][21][22] However, the key ligands and substituents of these models are classied with generic labels (e.g., 'strong p-acceptor', 'bulky' or 'proton-acceptor') that can be assigned to tens or hundreds of known compounds. The combination of all these possibilities yields a region of the chemical space 23 containing thousands of catalyst candidates.…”

Benchmarking of DFT methods using experimental free energies and volumes of activation for the cycloaddition of alkynes to cuboidal Mo3S4 clusters

“…In this sense, recent analyses have highlighted that obtaining reliable and predictive mechanistic insight from modeling remains challenging. [ 1,2 ] As the kinetic and mechanistic features of reactions are best evaluated by using activation parameters, an adequate refinement of computational methods for evaluating them is highly desired.…”

Unusual KIE and dynamics effects in the Fe-catalyzed hetero-Diels-Alder reaction of unactivated aldehydes and dienes

“…Computational chemistry has played a vital role in elucidating the mechanisms of organic reactions and helping design better catalysts and/or reactions [12][13][14][15][16][17][18][19][20] . Although many computational studies on the mechanism of DA and 1,3-dipolar cycloaddition reactions have been reported 3,4,6,[21][22][23][24][25][26] , computational works on the mechanism of HDA reactions are quite limited [27][28][29] .…”