Upon arrival to McMaster University during the outgoing phase, the researcher started to familarize with the quantum-chemical tools, methods and programs developed by the Ayers group. Electron densities and other descriptors for MEDT were computed and applied to several reactions. Then, new spin-resolved indicators for elucidating local electron-density changes and reactivity in non-polar reactions were developed.
Simultaneously, MEDT has also been applied to the study of several organic reactions together with the researcher's host group and various international collaborations to give it more visibility and credibility. Among them, epoxidation reactions, aromatic nucleophilic substitutions, nitration reactions, catalyzed and non-catalyzed Diels–Alder reactions, polar and non-polar [3+2] cycloaddition (32CA) reactions involving several several types of pseudodiradical, pseudomonoradical, carbenoid and zwitterionic reagents, aza-Diels-Alder reactions and ionic Diels-Alder reactions, were investigated.
During the secondment period, the researcher started to familiarize with the Interacting Quantum Atoms (IQA) approach, with the AIMAll software to perform the corresponding calculations, and with the in-house program for post-analysis of IQA using the reduced energy gradient (REG) method recently developed by Popelier’s group at the University of Manchester, and started to study the stereochemistry in a series of electrocyclic reactions.
Finally, during the returning period, the beneficiary applied the training received on quantum chemical tools during the outgoing phase to study diverse chemical processes, especially focusing on determining the factors contributing to reaction barriers within the MEDT perspective. By the end of the project, the researcher mastered the application of the IQA approach combined with the REG method, and was able to explain the origin of the energy costs of several chemical reactions. This is notoriously useful for syntheses designs, as one can select appropriate compound substitution in order to lower the factors contributing to the barrier and thus have quicker and/or more selective processes.
During the return period, electrophilic aromatic substitutions, intramolecular ionic Diels-Alder reactions, Lewis-acid catalyzed 32CA reactions, oxa-Diels-Alder reactions, the structure of a metallorganic complex, the behaviour of the Cr(CO)3 complex in Diels-Alder reactions, and the application of reactivity indices in polar Diels-Alder reactions and in chemical selectivity, have been studied.
These results have been disseminated in international conferences and in the fellow's host group website. In addition, the fellow has also commented on her successful case in an MSCA informative session at the host institution, encouraging future researchers to participate in the programme.
Overall, the 3-year project has contributed to the development of MEDT as a powerful paradigm that provides a modern rationalization of organic chemical reactivity based on the analysis of electron density. The MEDT interpretation contrasts with the traditional understanding based on widely known classical theories founded on the analysis of molecular orbitals and is allowing to build a completely different, yet more appropriate, picture of organic chemistry which will have a significant impact on future syntheses designs and applications.
