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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

New insights into the electrophilic aromatic substitution mechanism of tricyanovinylation reaction involving tetracyanoethylene and N,N-dimethylaniline: An interpretation based on density functional theory calculations

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Menezes da Silva, Vitor H. ; Monezi, Natalia M. ; Ando, Romulo A. ; Braga, Ataualpa A. C.
Total Authors: 4
Document type: Journal article
Source: Journal of Molecular Structure; v. 1142, p. 58-65, AUG 15 2017.
Web of Science Citations: 0

The reaction between tetracyanoethylene and N,N-dimethylaniline was extensively studied in early of 1960's. Surprisingly, the role of intermediate species involved in the reaction mechanism is still ambiguous. New density functional theory (DFT) calculations have been performed in order to elucidate such reaction pathways. The electrophilic addition of tetracyanoethylene was computed with a free energy barrier of 79 kJ mol(-1). The rate-determining step (RDS) of the reaction was observed during the base-assisted deprotonation process, with a calculated value of 103 kJ mol(-1). Finally, for the elimination reaction step was obtained a value at 70 kJ mol(-1). A strong influence of the solvent polarity has been corroborating the presence of a polar transition state for the RDS of this reaction. Nonpolar solvent provides a higher relative free energy barrier, which is in agreement with experimental observations. (C) 2017 Elsevier B.V. All rights reserved. (AU)

FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
Grantee:Ataualpa Albert Carmo Braga
Support Opportunities: Regular Research Grants
FAPESP's process: 15/11840-5 - Theoretical study on selectivity in Heck-Mizoroki reactions: comparisons between nickel and palladium catalytic systems
Grantee:Vitor Hugo Menezes da Silva
Support Opportunities: Scholarships abroad - Research Internship - Doctorate
FAPESP's process: 13/04813-6 - Mechanistic studies of Heck-Matsuda reactions: a theoretical investigation
Grantee:Vitor Hugo Menezes da Silva
Support Opportunities: Scholarships in Brazil - Doctorate
FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
Grantee:Carlos Roque Duarte Correia
Support Opportunities: Research Projects - Thematic Grants