Homolytic N–H bond cleavage in anilines: Energetics and substituent effect

Vagánek, Adam; Rimarčík, Ján; Ilčin, Michal; Škorňa, Peter; Lukeš, Vladimı́r; Klein, Erik

doi:10.1016/j.comptc.2013.03.027

Cited by 20 publications

(13 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For mono-substituted phenols, thiophenols and anilines, it has been found that B3LYP functional provided BDEs in very good accordance with available experimental and/or theoretical results , Rimarčík et al 2011, Vagánek et al 2013. PBE0 functional is able to provide bond cleavage energetics and physico-chemical properties of small and medium-size molecules in very good agreement with experimental data and computationally more demanding methods , Rimarčík et al 2008, Saracino et al 2003, Vagánek et al 2013, too. Calculations were performed in the 6-31G* (Rassolov et al 2001) and 6-311++G** (Binkley et al 1980) basis sets.…”

Section: Computational Detailssupporting

confidence: 64%

“…In the case of the model antioxidant compounds, the theoretical calculations allowed to extract some descriptors linearly correlating with BDEs. In the work of (C-N)) dependence, where R(C-N) is C-N bond length in substituted anilines, has been also assessed as satisfactory by Vagánek et al (Vagánek et al 2013). Although the literature clearly shows that number of theoretical and experimental studies focused on the homolytic C-H bond cleavage is low in comparison to reports on the N-H or O-H bond dissociation, importance of this process in biological systems is indisputable.…”

Section: • ) + H(h • ) -H(rh)mentioning

confidence: 99%

“…1 shows that the differences between B3LYP and PBE0 C-H BDE values are in the 2.5-7.2 kJ mol -1 range for both applied basis sets. Vagánek et al (Vagánek et al 2013) found that the differences between PBE0/6-311++G** N-H BDEs and B3LYP/6-311++G** N-H BDE values for the set of 42 paraand meta-substituted anilines are not larger than 2 kJ mol -1…”

Section: Calculation Of Bdesmentioning

confidence: 99%

See 2 more Smart Citations

Quantum-chemical study of C— H bond dissociation enthalpies of various small non-aromatic organic molecules

Poliak¹,

Vagánek²

2013

Acta Chimica Slovaca

Self Cite

View full text Add to dashboard Cite

In this work, C-H bond dissociation enthalpies (BDE) and vertical ionization potentials (IP) for various hydrocarbons and ketones were calculated using four density functional approaches. Calculated BDEs and IPs were correlated with experimental data. The linearity of the corresponding dependences can be considered very good. Comparing two used functionals, B3LYP C-H BDE values are closer to experimental results than PBE0 values for both used basis sets. The 6-31G* basis set employed with both functionals, gives the C-H BDEs closer to the experimental values than the 6-311++G** basis set. Using the obtained linear dependences BDE exp = f (BDE calc ), the experimental values of C-H BDEs for some structurally related compounds can be estimated solely from calculations. As a descriptor of the C-H BDE, the IPs and 13 C NMR chemical shifts have been investigated using data obtained from the B3LYP/6-31G* calculations. There is a slight indication of linear correlation between IPs and C-H BDEs in the sets of simple alkanes and alkenes/ cycloalkenes. However, for cycloalkanes and aliphatic carbonyl compounds, no linear correlation was found. In the case of the 13 C NMR chemical shifts, the correlation with C-H BDEs can be found for the sets of alkanes and cycloalkanes, but for the other studied molecules, no trends were detected.

show abstract

Section: Computational Detailssupporting

confidence: 64%

Section: • ) + H(h • ) -H(rh)mentioning

confidence: 99%

Section: Calculation Of Bdesmentioning

confidence: 99%

See 1 more Smart Citation

Quantum-chemical study of C— H bond dissociation enthalpies of various small non-aromatic organic molecules

Poliak¹,

Vagánek²

2013

Acta Chimica Slovaca

Self Cite

View full text Add to dashboard Cite

show abstract

“…The results of a previous study 44 showed that, instead of the properties of the phenolic O-H bond, the BDE of para-and meta-substituted phenols could be successfully correlated with the neighboring C-O bond length or with its shortening after hydrogen atom abstraction. Klein et al [44][45][46] found good linearity of ∆BDE vs. C-N bond length or its shortening after hydrogen atom abstraction for both, para-and meta-substituted anilines and also for N-H bond length vs. BDE. These geometric parameters represent suitable descriptors for substituent effects.…”

Section: The E Homo and R(o-h) Values Of The Studied Trolox Derivativesmentioning

confidence: 97%

“…In a previous study, the results for meta-substituted chromanes show that calculated BDE values could be successfully correlated with the lengths of the phenolic C-O bond of the studied chromanes. [44][45][46] In the present paper, the calculated values of the R(O-H) bond lengths corresponding to the studied Trolox derivatives are reported in Table IV…”

Section: The E Homo and R(o-h) Values Of The Studied Trolox Derivativesmentioning

confidence: 99%

Novel Trolox derivatives as antioxidant: A DFT investigation

Farmanzadeh

Najafi

2016

J Serb Chem Soc

View full text Add to dashboard Cite

In this paper, the antioxidant activity of 6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid (Trolox) derivatives were investigated by the density functional theory and the polarization continuum model as a solvent model in order to propose novel derivatives with a higher antioxidant activity from a theoretical viewpoint. The effects of various ortho and meta substituents on the reaction enthalpies of the antioxidant mechanisms of Trolox derivatives were investigated. In addition, the effect of reducing the number of atoms in the heterocyclic ring and the effect of replacing the oxygen heteroatom of Trolox with other heteroatoms on the antioxidant activity of Trolox derivatives were evaluated. The results showed that NH 2 , OH and NHMe substituents in the meta and ortho positions decreased the homolytic bond dissociation enthalpy (BDE) and adiabatic ionization potential (IP) values and increased the antioxidant activities of the Trolox derivatives from the theoretical viewpoint. The derivatives e, c and d with NH, S and Se instead of O, respectively, had higher antioxidant activities from the theoretical viewpoint. The obtained results showed that reducing the number of atoms in the heterocyclic ring (derivatives a and b) decreased the BDE and IP values and increased the antioxidant activities of the Trolox derivatives from the theoretical viewpoint. The linear dependencies between BDE of the O-H bond and IP values of the studied Trolox derivatives and the corresponding E HOMO and R(O-H) values could assist in the proposal of novel derivatives with higher antioxidant activity from the theoretical viewpoint.Истраживано је антиоксидативно дејство деривата тролокса помоћу теорије функционала густине и модела растварача као поларизационог континуума како би се са теоријске тачке гледања могли предложити нови деривати са вишом антиоксидативном активношћу. Истраживани су ефекти различитих ortho и meta супституената тролокса на _________________________________________________________________________________________________________________________ Available on line at www.shd.org.rs/JSCS/ (CC) 2016 SCS. All rights reserved.

show abstract

Substituent effects on the antioxidant capacity of monosubstituted diphenylamines: a DFT study

Thảo

Thong

et al. 2020

Vietnam Journal of Chemistry

View full text Add to dashboard Cite

There are undesirable effects leading to considerable changes in the properties of polymers and plastics since exposing to oxygen undergo oxidative degradation. Therefore, investigation of the bond dissociation enthalpies (BDEs) of N‐H bond for a series of monosubstituted diphenylamines is great interest. In this study, DFT‐based method B3P86/6‐311G was employed to perform this task. In comparison with the available experimental data, this method could reproduce the BDE(N‐H)s values more accuracy. Effects of substituents and substitution positions on the BDE(N‐H)s were also examined. Moreover, there is a good correlation of BDE(N‐H)s with the Hammett's substituent constants. Depending on the nature of substituents, electron withdrawing groups increase the BDE(N‐H)s but electron donating ones reduce the BDE(N‐H)s. The hydrogen atom transfer processes from N‐H bond of these diphenylamines to the peroxyl radical (CH3OO•) were also analyzed via potential energy surfaces and kinetic calculations.

show abstract

Homolytic N–H bond cleavage in anilines: Energetics and substituent effect

Cited by 20 publications

References 56 publications

Quantum-chemical study of C— H bond dissociation enthalpies of various small non-aromatic organic molecules

Quantum-chemical study of C— H bond dissociation enthalpies of various small non-aromatic organic molecules

Novel Trolox derivatives as antioxidant: A DFT investigation

Substituent effects on the antioxidant capacity of monosubstituted diphenylamines: a DFT study

Contact Info

Product

Resources

About