A Theoretical Investigation on the Aminolysis of Pyromellitic and 1,4,5,8-Naphthalenetetracarboxylic Dianhydrides

Publication date: Available online 20 November 2018Source: Computational and Theoretical ChemistryAuthor(s): Felipe S.S. Schneider, Jeffry Setiadi, Maria Isabel Felisberti, Pedro A.M. Vazquez, Thiago Ferreira da Conceição, Germano Heinzelmann, Giovanni Finoto CaramoriAbstractAniline aminolysis reaction of pyromellitic (PMDA) and 1,4,5,8-naphthalenetetracarboxylic (NTDA) dianhydrides is investigated by means of density functional theory (BP86-D3(BJ)/def2-TZVP). The concerted mechanism is shown to be more favorable for both substrates, in comparison to the stepwise one, with the aminolysis of PMDA presenting lower activation energy than the reaction of NTDA. This result is shown to be related to the lower ring tension in NTDA. Solvation also shows significant influence on the kinetics and thermodynamics of these reactions, as determined by two different methods, implicit with the universal solvation model SMD, and explicit with alchemical FEP molecular dynamics simulations. The comparison between SMD and FEP enables us to explore possible inaccuracies on the SMD model, and examine the suitability of the FEP approach as a physics-based method for the calculation of the solvent contribution in different reactions.Graphical abstract

Source: Computational and Theoretical Chemistry - November 21, 2018 Category: Chemistry Source Type: research