TAILIEUCHUNG - Bond dissociation enthalpies in benzene derivatives and effect of substituents: an overview of density functional theory (B3LYP) based computational approach
In this review, we have mainly focused on the recent computational studies on the bond dissociation enthalpies (BDE) of the X‒H bonds of the para and meta substituted benzene derivatives (3Y-C6H4X‒H and 4Y-C6H4X‒H with X = O, S, Se, NH, PH, CH2, SiH2 and Y = H, F, Cl, CH3, OCH3, NH2, CF3, CN, NO2). | Vietnam Journal of Chemistry, International Edition, 55(6): 679-691, 2017 DOI: Invited review Bond dissociation enthalpies in benzene derivatives and effect of substituents: an overview of density functional theory (B3LYP) based computational approach Pham Cam Nam1*, Vo Van Quan2, Nguyen Minh Thong3, Pham Thi Thu Thao4,5 Department of Chemistry, The University of Danang – University of Science and Technology 1 2 Department of Natural Sciences, Quang Tri Teachers Training College 3 The University of Danang, Campus in Kon Tum 4 Hue University of Sciences, Hue University 5 Le Quy Don gifted high school in Quang Tri Received 27 October 2017; Accepted for publication 29 December 2017 Abstract In this review, we have mainly focused on the recent computational studies on the bond dissociation enthalpies (BDE) of the X‒H bonds of the para and meta substituted benzene derivatives (3Y-C6H4X‒H and 4Y-C6H4X‒H with X = O, S, Se, NH, PH, CH2, SiH2 and Y = H, F, Cl, CH3, OCH3, NH2, CF3, CN, NO2). In addition, the remote substituent effects on the BDE(X‒H), the radical stability and parent one have also been discussed in terms of the calculated ground state effect, radical effect and total effect. Model chemistry of ROB3LYP/6-311++G(d,p)//B3LYP/6-311G(d,p) can reproduce the BDE values with the accuracy of ‒ kcal/mol. The good linear correlations between Hammett constants and BDE values were discovered for both para and meta substitutions in phenols, thiophenols, benzeneselenols, anilines and phenylposphines with the R-squared lager than . In contrast, it does not occur in case of toluenes and phenylsilanes. Keywords. Benzene derivatives, density functional theory, bond dissociation enthalpies, substituent effects, radical effect, ground state effect, total effect, Hammett constants. 1. INTRODUCTION The chemistry of benzene derivatives, especially in phenol, thiophenol, benzeneselenol, aniline, phenylphosphine, toluene, .
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