Experimental versus Calculated Proton Affinities for Aromatic Carboxylic Acid Anions and Related Phenide Ions

Błaziak, Kacper; Sendys, Przemysław; Danikiewicz, Witold

doi:10.1002/cphc.201501101

Cited by 3 publications

(2 citation statements)

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“…Molecules 2020, 25, x 8 of 16 [58,59]. These values are very close to available experimental data for pyridine (930 kJ/mol) [60,61], collidine (980 kJ/mol) [61], benzoate (1422 kJ/mol) and 2-nitrobenzoate (1383 kJ/mol) [62], formate (1445 kJ/mol) and acetate (1456 kJ/mol) [63], and fluoride (1550 kJ/mol) [64]. Figure 6 demonstrates the lower limits of the external electric field simulated the effect of CDF3/CDClF2 on 2-6 under the PCM (Figure 6a) and gas-phase (Figure 6b) approximations as a function of the PA of the involved conjugate bases.…”

Section: Discussionsupporting

confidence: 85%

“…The easiest way to estimate the proton-donating and proton-accepting powers is to calculate the gas-phase proton affinity (PA), Table 4 [58,59]. These values are very close to available experimental data for pyridine (930 kJ/mol) [60,61], collidine (980 kJ/mol) [61], benzoate (1422 kJ/mol) and 2-nitrobenzoate (1383 kJ/mol) [62], formate (1445 kJ/mol) and acetate (1456 kJ/mol) [63], and fluoride (1550 kJ/mol) [64].…”

Section: Discussionsupporting

confidence: 62%

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Adduct under Field—A Qualitative Approach to Account for Solvent Effect on Hydrogen Bonding

Shenderovich

Денисов

2020

Molecules

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The location of a mobile proton in acid-base complexes in aprotic solvents can be predicted using a simplified Adduct under Field (AuF) approach, where solute–solvent effects on the geometry of hydrogen bond are simulated using a fictitious external electric field. The parameters of the field have been estimated using experimental data on acid-base complexes in CDF3/CDClF2. With some limitations, they can be applied to the chemically similar CHCl3 and CH2Cl2. The obtained data indicate that the solute–solvent effects are critically important regardless of the type of complexes. The temperature dependences of the strength and fluctuation rate of the field explain the behavior of experimentally measured parameters.

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Section: Discussionsupporting

confidence: 85%

Section: Discussionsupporting

confidence: 62%

Adduct under Field—A Qualitative Approach to Account for Solvent Effect on Hydrogen Bonding

Shenderovich

Денисов

2020

Molecules

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Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

Franczuk

Danikiewicz

2018

J. Am. Soc. Mass Spectrom.

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Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction (m/z 47), SN2 (m/z 79), and E2 elimination – addition sequence of reactions (m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. Graphical Abstractᅟ Electronic supplementary materialThe online version of this article (10.1007/s13361-017-1858-x) contains supplementary material, which is available to authorized users.

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Tautomeric equilibrium, proton affinity and mass spectrometry fragmentation of flexible hydrogen-bonded precursors and rigid $$\hbox {N}\longrightarrow \hbox {BF}_2$$ fluorescent dyes

Kaczorowska

Kaczmarek‐Kędziera

Ośmiałowski

2021

Sci Rep

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The stability of two groups of conformationally locked molecules, similar in topology, but differing only by the type of the bridge rigidifying their structure, is studied. The series of the less-rigid 2-phenacylheterocyclic compounds and their stiff difluoroboranyl derivatives are investigated for the determination of the effect of $$\hbox {NCH}_3$$ NCH 3 /S/O replacement in a five-membered heterocyclic ring and the presence of a strong electron-donating group on the tautomeric equilibrium, protonation affinity, and fragmentation pattern observed in the structural elucidation by means of mass spectrometry technique. The results of the $$\omega $$ ω B97X-D/6-311++G(d,p) calculations, the topological analysis of electron density as well as the experimental MS measurements show the importance of the number of heteroatoms, their properties, and location in the molecule for the rational design of the systems of desired stable tautomers or the favorable protonation sites. The obtained data allow for the understanding of the fundamentals of the novel highly fluorescent difluoroborates fragmentation behavior, vital for their structural elucidation with the application of high-resolution tandem mass spectrometry methods.

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Experimental versus Calculated Proton Affinities for Aromatic Carboxylic Acid Anions and Related Phenide Ions

Cited by 3 publications

References 44 publications

Adduct under Field—A Qualitative Approach to Account for Solvent Effect on Hydrogen Bonding

Adduct under Field—A Qualitative Approach to Account for Solvent Effect on Hydrogen Bonding

Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

Tautomeric equilibrium, proton affinity and mass spectrometry fragmentation of flexible hydrogen-bonded precursors and rigid $$\hbox {N}\longrightarrow \hbox {BF}_2$$ fluorescent dyes

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