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WIREs Comput Mol Sci
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Structure–reactivity relationships for aromatic molecules: electrostatic potentials at nuclei and electrophile affinity indices

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Abstract Recent advances have been achieved in the quantitative description of the reactivity of aromatic compounds in terms of simple parameters derived from theoretical computations. The first part of this review surveys the use of electrostatic potentials at nuclei (EPN) in characterizing the reactivity of substituted aromatic compounds when the reaction center is situated outside the aromatic ring. The application of EPN for several typical reactions of substituted aromatic systems is described in detail. The performance of alternative reactivity descriptors, such as theoretical atomic charges, the Parr electrophilicity index, and the experimental Hammett constants, is considered as well. The second part of this review discusses the recently proposed electrophile affinity construct for quantifying reactivity and regiospecificity for the most typical reaction of arenes: electrophilic aromatic substitution. The characterization of reactivity of aromatic molecules in terms of proton affinities and arene nucleophilicity indices is surveyed briefly. This article is categorized under: Structure and Mechanism > Molecular Structures

Nucleophilicity parameters (Methods I–IV) versus Hammett substituent constants (σp) for arenes investigated in Ref 87.

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Rates of protiodetritiation compared to MP2/6‐31G*//HF/6‐31G* proton affinities for benzene, naphthalene, phenanthrene, and anthracene (BNPA).85

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Electrophile affinities (solv) versus experimental log krel kinetic data84 for a set of 37 bromination reactions of benzene and variously substituted derivatives.

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Partial rate factor (log f) versus electrophile affinity () for the chlorination of benzene and methyl benzenes.

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B3LYP/6‐311+G(2d,2p) optimized structure of the C6H6Cl+ σ complex (Cs symmetry).

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The direct mechanism of sulfonation of benzene with two SO3 molecules in the gas phase or in nonpolar media. (Reprinted with permission from Ref 81. Copyright 2011 American Chemical Society.)

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The concerted and addition‐elimination AE pathways of bromination of benzene in isolation (gas phase) or in nonpolar media.

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The SEAr mechanism of electrophilic aromatic substitution: a reaction mechanism paradigm for arenes.

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Dependence between experimental fluorescence maxima in acetonitrile solution and theoretically obtained (PCM PBE0/6‐31+G(d)) EPN values at the naphthalimide nitrogen in the excited states of aryl hydrazones.

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Substituted aryl hydrazones of 1,8‐naphthalimide whose spectral characteristics have been related to electronic indices.78

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Polyfluorosubstituted 1,3,5‐triarylpyrazolines investigated by Fahrni and co‐workers.77 (Reproduced by permission of the Royal Society of Chemistry.)

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Correlation between σR0 and EPN‐derived σRv values.

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Dependence between the theoretical electrostatic potential at the meta‐ and para‐carbon atoms in monosubstituted benzenes and the σ0 constants.

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Relationship between the net SN2 activation barrier (Eb) and the reaction‐center electrostatic potential (VC) for the substituted benzyl fluorides of Scheme 4. VC is plotted for the central carbon atom in the isolated reactant (A) and the SN2 transition state (TS) (B).

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Identity SN2 reactions analyzed for the benzylic effect. (Reprinted with permission from Ref 58. Copyright 2008 American Chemical Society.)

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Energy profile of SN2 identity exchange reactions of benzyl derivatives. (Reprinted with permission from Ref 58. Copyright 2008 American Chemical Society.)

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Plots between barrier heights for the water‐assisted N‐ (A) and O‐pathways (B) and the electrostatic potential at the C2 and C5 atoms.54

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Acid‐promoted hydrolysis of 2‐aryloxazolin‐5‐ones.54

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Plot between ln k values for the alkaline hydrolysis of acetanilides and their electrostatic potentials at the amide nitrogen atoms (VN, in volts).

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General scheme of reactions studied for hydrolysis of acetanilides. (Reprinted with permission from Ref 49. Copyright Taylor & Francis.)

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Experimental rate constants (ln k) for the n‐butylaminolysis of substituted phenyl acetates plotted against reactivity descriptors.

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Correlation between barrier heights for the concerted pathway of phenyl acetate aminolysis and the electrostatic potential at the reactant ester carbonyl carbon atoms.

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Series of aminolysis reactions of phenyl acetate derivatives.46

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Correlation between nucleophilicity parameters N and Hammett σ+ constants.

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