R. W. Taft’s research while affiliated with University of California, Irvine and other places

... Quantum-chemical calculations (AM1, HF, MP2, DFT), performed for N,N-dimethylaminoacrylonitrile and N 1 ,N 1dimethyl-N 2 -cyanoformamidine, confirmed that the cyano nitrogen atom is the favored site of protonation. 32,172,321 It is also the favored site for H-bonding. 322 Experimental GB determinations and quantum-chemical calculations (Gn and DFT), performed for unsubstituted aminoacrylonitrile (H 2 N−CHCH−CN), showed without any doubt that protonation takes place at the cyano nitrogen atom. ...

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Enhanced Basicity of Push-Pull Nitrogen Bases in the Gas Phase

... According to this study, COSMO-RS predicted E HB to have a substantial correlation with experimental hydrogen bonding basicity. Hydrogen bonding basicity is known as the capacity of ionic liquids to take in hydrogen atoms [197]. Klamt [198] established the principle of interaction between water and solute molecules using COSMO-RS to determine their sigma-profiles and sigmapotentials. ...

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Chemical Inhibitors in Gas Hydrate Formation: A Review of Modelling Approaches

... They govern the way chemists steer organic reactions, activate reactants, stabilize intermediates, transition states, or products. [1][2][3][4][5][6] They are central to the identi cation of reaction mechanisms, also in biochemistry, indispensable when we draw electron-pushing arrows, and they have driven the eld of quantitative structure-activity relationships on which large parts of physical-organic and medicinal chemistry are founded upon. 7 Substituent effects are equally relevant for the engineering of organic and polymeric electronic as well as optical materials, and ne-tuned electron-withdrawing as well as -donating effects have driven the early development of industrial dye chemistry. ...

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The Hammett substituent constant of the dodecaborate dianion inaugurates a non-coordinating, non-basic, and strongly inductively electron-donating group for organic chemistry

... For this reason, the knowledge how cyclic ethers interact with organic solvent molecules is of paramount importance. Many papers have dealt with the effect of the properties of pure[12][13][14][15]and mixed (organic ? organic and organic ? ...

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Effect of properties of the N,N-dimethylformamide + methanol and N,N-dimethylformamide + water mixtures on the solution enthalpy of cyclic ethers in these mixtures at 298.15 K

... For instance, protic hydrogen atom donors like phenols are less reactive in terms of hydrogen atom transfer in polar media because of the their hydrogen bonding ability [37]. Thiols are less sensitive to hydrogen bonding due to fact that they are weak hydrogen bond donors [38]. In contrast to that, it has been shown that polar solvents especially water increase the rate of hydrogen atom transfer to alkyl radical. ...

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Kinetic and Thermodynamic Aspects of Reactions Involving Thiyl Radicals: A Computational Approach

... The linear solvation energy relationships method is one of the most successful approaches where empirical or experimentally determined solvent parameters, such as the solvent solvatochromic parameters, are used to quantify the effect of solvents on chemical reactions. 35,36 This method can generally provide satisfactory predictions of the rates of a specific reaction in some prespecified solvents. However, it can neither be directly applied for extensive solvent screening nor for solvent design, because the required parameters are available for a limited number of solvents only. ...

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Integrated Solvent and Process Design Exemplified for a Diels-Alder Reaction

... The dipole moments of the ground as well as excited state" singlet are determined by employing the solvatochromic value of the given Coumarin derivative in various solvents with different polarity and hydrogen bonding properties. The outcomes of the experiment are "examined using Lippert and Mataga's bulk solvent polarity [13,14], Reichardt's microscopic solvent polarity parameter [15], and the solvatochromic parameters put forth by Kamlet et al. [16][17][18] and Catalan and colleagues [19]. Independent equations were used to calculate the dipole moments of the ground and excited states of" the 6MNPM derivative. ...

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Estimation of Electric Dipole Moment by Solvatochromism, Computational Method, and Study of the Effect of Solvents by Preferential Solvation of 6 – Methoxy—4—(4—Nitro—Phenoxy Methyl)—Chromen—2—One (6mnpm)

... Generally, the gas-phase acidity of a Bronsted acid is defined as the Gibbs free energy, ΔG, of the deprotonation reaction 1. 49 In most studies involving negative ion photoelectron spectroscopy, the negative ion thermochemistry cycle is utilized to relate the bond-dissociation energy of a molecule with gas-phase acidity and EA of the radical. 50 In such scenarios, the gas-phase acidity is defined as the deprotonation enthalpy, ΔH, of reaction 1 and is indirectly derived using eq 4 since, in most instances, the quantities on the right-hand side of eq 4 are known from spectroscopic data with known experimental uncertainties. ...

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From Benzonitrile to Dicyanobenzenes: The Effect of an Additional CN Group on the Thermochemistry and Negative Ion Photoelectron Spectra of Dicyanobenzene Radical Anions

... Worth mentioning is that complexes of a polymerizable amidine, N,N'-diethyl-4-vinylbenzamidine, and a phosphonate template were recently used in the preparation of molecularly imprinted polymers [353] that, by mimicking catalytic antibodies, were able to hydrolyse esters. Amidines are relatively unexplored with regards to their energetics [354]: nonetheless, there are patterns suggested for their basicity [355] and their enthalpy of formation [356]. ...

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Interplay of thermochemistry and Structural Chemistry, the journal (volume 17, 2006) and the discipline

... Thus, several multiparametric equations have been developed that combine two or more solvent parameters to explain the particular and distinctive aspects of the solvent effect on a given compound, among them, those of Kamlet and Taft,12,13 Catalán 40 and Laurence 41 are the most employed. 27,[39][40][41] Regarding all existing solvent polarity scales, the empirical solvatochromic scale of Kamlet and Taft [42][43][44][45][46] stands out, based on the linear solvation energy relationships (LSER). 39,[42][43][44][45][46] The Kamlet and Taft 44 method rationalize the effect of the solvent in terms of a linear combination of three variables: the parameter p* refers to the shared effect of the polarity-polarizability of the solvent, which measures the ability of the environment to stabilize the charges of a dipole due to its dielectric effects. ...

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Solvatochromism and Thermochromism of Fluconazole: An Experimental and Theoretical Study