Substituent effects in some autoxidation and hydrogen abstraction reactions in terms of their field (F) and resonance (R) components inclusive of unique positional weighting factors

1980 ◽  
Vol 58 (24) ◽  
pp. 2754-2760 ◽  
Author(s):  
Lalit N. Patnaik ◽  
Nigamananda Mallick ◽  
M. K. Rout ◽  
Swoyam P. Rout
Keyword(s):  
Transition State ◽  
Hydrogen Abstraction ◽  
Substituent Effects ◽  
Reference Compound ◽  
General Validity ◽  
Correlation Studies ◽  
Weighting Factors ◽  
Benzyl Radical ◽  
Resonance Stabilization ◽  
Stabilization Energies

Substituent effects in some autoxidation and hydrogen abstraction reactions have been studied in terms of the field (Fk) and resonance (Rk) components proposed by Swain and Lupton and the unique positional weighting factors fj and rj incorporated by Williams and Norrington with the aid of the following equation:[Formula: see text]where Pi's are the rate parameters, Pi0 being that for a standard reference compound. The correlations are found to be quite satisfactory, showing the general validity of the above equation for the types of reactions considered. From the information obtained from the present correlation studies, an attempt has been made to resolve the conflict with regard to the nature of the transition state involved in the hydrogen abstraction reactions – that is, whether or not there is charge separation in the transition state. The results of the present studies seem to suggest that both the differences in the resonance stabilization energies of the ring-substituted benzyl radical and the contribution of polar structures to the transition state are to be invoked to explain the observed data.

Molecular orbital treatment of substituent effects. I. Structures of some carbon acids and their conjugate bases

1983 ◽  
Vol 61 (1) ◽  
pp. 45-49 ◽  
Author(s):  
Kenneth E. Edgecombe ◽  
Russell J. Boyd
Keyword(s):  
Molecular Orbital ◽  
Substituent Effects ◽  
Stabilization Energy ◽  
Basis Set ◽  
Carbon Acids ◽  
Resonance Stabilization ◽  
Stabilization Energies ◽  
Conjugate Bases ◽  
Equilibrium Geometries

The STO-3G optimized structures of three series of carbon acids, CHnX4−n, where n = 1, 2, or 3 and X = F, CN, or NO2 and their corresponding conjugate bases are compared with the limited number of experimentally determined structures. The 6-31G* equilibrium geometries of [Formula: see text] are included as a check on the reliability of the STO-3G structures of the anions. Although the effects of successive substitutions on the STO-3G structures are generally systematic, a few apparent anomalies are readily explained in terms of resonance stabilization. Calculations at the 3-21G level, on the STO-3G optimized structures, indicate that the stabilization energy associated with increasing the number of orbitals in the basis set is approximately additive. The stabilization energies are 0.865 ± 0.007 au per fluorine substituent, 0.661 ± 0.008 au per cyano substituent, and 1.561 ± 0.027 au per nitro substituent.

The aromatic character and resonance stabilization energies of substituted cyclopentadienyl and indenyl cations

2005 ◽  
Vol 83 (9) ◽  
pp. 1287-1298 ◽  
Author(s):  
J A Pincock ◽  
A WH Speed
Keyword(s):  
Triplet State ◽  
Bond Length ◽  
Positive Charge ◽  
Singlet State ◽  
Substituent Effects ◽  
Bond Alternation ◽  
Carbon Carbon Bond ◽  
Resonance Stabilization ◽  
Stabilization Energies ◽  
Electron Donating Groups

Calculations (B3LYP/6-31G(d)) have been used to assess the aromaticity of 5-X substituted indenyl (4) and cyclopentadienyl (5) cations with X = O–, NH2, OCH3, CH3, F, H, CN, and N2+. Two criteria were used, the aromatic stabilization energy (ASE), as determined by isodesmic reactions, and bond alternation, as determined from the Julg index (A) on the basis of carbon–carbon bond lengths. Substituent effects on the singlet state of the cyclopentadienyl cations resulted in significant decreases in antiaromatic character for electron-donating groups as indicated by larger A values (A = –0.25 for X = H and +0.26 for X = NH2). These decreases paralleled increases in the C-2—C-3 bond length and good linear correlations were obtained between A vs. the C-2—C-3 bond length and A vs. the ASE. These effects were rationalized by the stabilization by the electron-donating groups of the positive charge at C-5 generated as a consequence of a Jahn–Teller distortion leading to a lowest energy singlet state with a HOMO of a2 symmetry. In contrast, the lowest energy triplet state for each of the substituted cyclopentadienyl cations has little bond alternation (A > 0.9) and, by this criterion, is not significantly antiaromatic. The triplet state is more stable than the singlet state for the unsubstituted case and those with electron-withdrawing groups (ΔEST = –11.3 and –9.3 kcal/mol for X = H and CN, respectively) (1 cal = 4.184 J), but less stable for electron-donating groups (ΔEST = +15.0 kcal/mol for X = NH2). For the indenyl cations 4, the ASE values were almost independent of the substituent and the A values only decreased slightly for electron-donating groups. The A values also indicated that the indenyl cations could be divided into two moieties, an X-substituted pentadienyl cation with considerable delocalization and little bond alternation, and a 2,3-butadiene one with considerable bond alternation. This separation also placed the major portion of the positive charge on the pentadienyl part. The lack of symmetry in the substituted indenyl cations rationalizes the selective reactivity of the 5-methoxy-substituted cation at C-1. Finally, the resonance stabilization energies (RSE) of the substituted cations gave a linear correlation with the RSEs of 4-substituted benzylic cations.Key words: indenyl cations, cyclopentadienyl cations, substituent effects, stabilization energies.

A Reinvestigation of the Deceptively Simple Reaction of Toluene with ●OH, and the Fate of the Benzyl Radical. I. a Combined Thermodynamic and Kinetic Study on the Competition Between ●OH Addition and Hydrogen Abstraction Reactions.

2019 ◽  
Author(s):  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Marc E. Segovia ◽  
Martina Kieninger ◽  
Oscar Ventura ◽  
...  
Keyword(s):  
Density Functional ◽  
Room Temperature ◽  
Hydrogen Abstraction ◽  
Reaction Rates ◽  
Composite Model ◽  
Alternative Mechanism ◽  
Radical Intermediate ◽  
Experimental Conditions ◽  
Methyl Group ◽  
Benzyl Radical

This work reports density functional and composite model chemistry calculations performed on the reactions of toluene with the hydroxyl radical. Both experimentally observed H-abstraction from the methyl group and possible additions to the phenyl ring were investigated. Reaction enthalpies and heights of the barriers suggest that H-abstraction is more favorable than ●OH addition to the ring. The calculated reaction rates at room temperature and the radical-intermediate product fractions support this view. This is somehow contradictory with the fact that, under most experimental conditions, cresols are observed in a larger concentration than benzaldehyde. Since the accepted mechanism for benzaldehyde formation involves H-abstraction, a contradiction arises that begs for an explanation. In this first part of our work we give the evidences that support the preference of hydrogen abstraction over ●OH addition and suggest an alternative mechanism which shows that cresols can actually arise also from the former reaction and not only from the latter.

A Reinvestigation of the Deceptively Simple Reaction of Toluene with ●OH, and the Fate of the Benzyl Radical. I. a Combined Thermodynamic and Kinetic Study on the Competition Between ●OH Addition and Hydrogen Abstraction Reactions.

2019 ◽  
Author(s):  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Marc E. Segovia ◽  
Martina Kieninger ◽  
Oscar Ventura ◽  
...  
Keyword(s):  
Density Functional ◽  
Room Temperature ◽  
Hydrogen Abstraction ◽  
Reaction Rates ◽  
Composite Model ◽  
Alternative Mechanism ◽  
Radical Intermediate ◽  
Experimental Conditions ◽  
Methyl Group ◽  
Benzyl Radical

This work reports density functional and composite model chemistry calculations performed on the reactions of toluene with the hydroxyl radical. Both experimentally observed H-abstraction from the methyl group and possible additions to the phenyl ring were investigated. Reaction enthalpies and heights of the barriers suggest that H-abstraction is more favorable than ●OH addition to the ring. The calculated reaction rates at room temperature and the radical-intermediate product fractions support this view. This is somehow contradictory with the fact that, under most experimental conditions, cresols are observed in a larger concentration than benzaldehyde. Since the accepted mechanism for benzaldehyde formation involves H-abstraction, a contradiction arises that begs for an explanation. In this first part of our work we give the evidences that support the preference of hydrogen abstraction over ●OH addition and suggest an alternative mechanism which shows that cresols can actually arise also from the former reaction and not only from the latter.

Nucleophilic cleavage of diaryl disulphides

1973 ◽  
Vol 26 (1) ◽  
pp. 121 ◽  
Author(s):  
DAR Happer ◽  
JW Mitchell ◽  
GJ Wright
Keyword(s):  
Transition State ◽  
Reaction Rate ◽  
Substituent Effects ◽  
Butyl Alcohol ◽  
Sulphur Atom ◽  
Cyanide Ion ◽  
Benzene Rings ◽  
Nucleophilic Cleavage ◽  
Rapid Equilibrium ◽  
Electron Withdrawal

The rates of cleavage of 14 symmetrically substituted diaryl disulphides by cyanide ion have been measured in 60% aqueous t-butyl alcohol at pH 9.2. A plot of log k against σ� shows that while the reaction rate is accelerated by inductive electron withdrawal from the benzene rings, substituents capable of conjugative interaction are not correlated by their σ� parameters. +R substituents cause reaction to occur much faster than predicted on the basis of their σ� values, while -R substituents react more slowly than predicted. Measurement of rates of cleavage of three series of unsymmetrically substituted disulphides by cyanide or hydroxide shows that these unusual substituent effects arise from substituents in the thiocyanate-forming aryl ring. This behaviour is explained in terms of a change in the electronic behaviour of the thio- cyanate-forming sulphur atom from -I, + R in the disulphide to -I,-R in the rate-determining transition state for the reaction. The study does not show whether the cleavage involves an SN2 process or rapid equilibrium formation of a pentacovalent intermediate.

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