期刊
MOLECULES
卷 22, 期 5, 页码 -出版社
MDPI
DOI: 10.3390/molecules22050750
关键词
azomethine imine; [3+2] cycloaddition reactions; molecular electron density theory; conceptual density functional theory; electron localisation function; bonding evolution theory; electron density; molecular mechanisms; chemical reactivity
资金
- Ministry of Economy and Competitiveness (MINECO) of the Spanish Government (AEI/FEDER, UE) [CTQ2016-78669-P]
- MINECO - European Social Fund [BES-2014-068258]
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+ 2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using Density Functional Theory (DFT) calculations at the MPWB1K/6-311G(d) level. Topological analysis of the electron localisation function reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterises this three-atom-component (TAC) as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with moderate activation energy, 8.7 kcal.mol(-1). A bonding evolution theory study indicates that this reaction takes place through a non-concerted [2n + 2 tau] mechanism in which the C-C bond formation is clearly anticipated prior to the C-N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the activation energy is only 0.4 kcal.mol(-1), in complete agreement with the high polar character of the more favourable regioisomeric transition state structure. The current MEDT study makes it possible to extend Domingo's classification of 32CA reactions to a new pseudo(mono) radical type (pmr-type) of reactivity.
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