Hydrogen Bonds and the Reactivity of Organic Compounds in Proton Transfer and Nucleophilic Substitution Reactions

Épshtein, L. M.

doi:10.1070/rc1979v048n09abeh002417

Cited by 40 publications

(14 citation statements)

References 2 publications

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“…[34] There is an empirical linear dependence between gas-phase and solution pK a values within the same class of acids, [35,37,38] which is possible due to the fact that the free energy difference between an acid and ab ase is attenuated by differential solvation effects that are specific for the acid class,e lectric charge and solvent. Such correlations have been documented for phenols, [39] alcohols, [38,40] amines, [41] thiols, [41] and CH-acids. [42,43] In this way,t he gasphase pK a of 177.7 calculated for 2 can be compared to the gas-phase pK a of other cationic silanes described by Krempner and co-workers (Figure 1B), [12] which we calculate as being 205.5 for M = Kand 197.8 for M = Li (Section S5.1.4).…”

Section: Computational Analysis Of Acidity Of [Tsmpsih] + (2)mentioning

confidence: 70%

Strain‐Modulated Reactivity: An Acidic Silane

et al. 2021

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Compounds of main‐group elements such as silicon are attractive candidates for green and inexpensive catalysts. For them to compete with state‐of‐the‐art transition‐metal complexes, new reactivity modes must be unlocked and controlled, which can be achieved through strain. Using a tris(2‐skatyl)methylphosphonium ([TSMPH3]+) scaffold, we prepared the strained cationic silane [TSMPSiH]+. In stark contrast with the generally hydridic Si−H bond character, it is acidic with an experimental pKaDMSO within 4.7–8.1, lower than in phenol, benzoic acid, and the few hydrosilanes with reported pKa values. We show that ring strain significantly contributes to this unusual acidity along with inductive and electrostatic effects. The conjugate base, TSMPSi, activates a THF molecule in the presence of CH‐acids to generate a highly fluxional alkoxysilane via trace amounts of [TSMPSiH]+ functioning as a strain‐release Lewis acid. This reaction involves a formal oxidation‐state change from SiII to SiIV, presenting intriguing similarities with transition‐metal‐mediated processes.

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Section: Computational Analysis Of Acidity Of [Tsmpsih] + (2)mentioning

confidence: 70%

Strain‐Modulated Reactivity: An Acidic Silane

et al. 2021

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“…Electron interactions and the formation of strong hydrogen bonds by hydroxyl and/or carboxyl groups impact the physicochemical properties of phenolic acids [14][15][16][17][18][19]. It should be mentioned, that carboxylic acids differ from the phenols by the reactivity in proton transfer processes, the hydrogen bond strength and the structure in self-associates and complexes with electron-donors [20]. So, these processes are expected to result in the distinction of polyphenol and phenolic acid adsorption properties.…”

Section: Introductionmentioning

confidence: 97%

Interactions between bioactive ferulic acid and fumed silica by UV–vis spectroscopy, FT-IR, TPD MS investigation and quantum chemical methods

Kulik

Lipkovska

Барвинченко

et al. 2009

Journal of Colloid and Interface Science

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“…In fact, it should be remarked that N···H d is the shortest hydrogen bond, which corroborates protonation of the aziridine [75]. Of course, this is not absolutely conclusive, but it is fair to say that formation of the hydrogen bonds provides some interesting insights into chemical reactivity [76].…”

Section: Structurementioning

confidence: 87%

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Oliveira

Araújo

2011

J Mol Model

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B3LYP calculations, ChelpG atomic charges, and quantum theory of atoms in molecules (QTAIM) integrations were used to investigate the binary (1:1) and ternary (1:2) hydrogen-bonded complexes formed by aziridine (1) and ammonia (2). In a series of analysis, geometry data, electronic parameters, vibrational oscillators, and topological descriptors were used to evaluate hydrogen bond strength, and additionally to determine the more prominent molecular deformations upon the formation of C(2)H(5)N···NH(3) (1:1) and C(2)H(5)N···2NH(3) (1:2) systems. Taking a spectroscopic viewpoint, results obtained from analysis of the harmonic infrared spectrum were examined. From these, new vibrational modes and red- and blue-shifts related to the stretch frequencies of either donors or acceptors of protons were identified. Furthermore, the molecular topology of the electronic density modeled in accord with QTAIM was absolutely critical in defining bond critical points (BCP) and ring critical points (RCP) on the heterocyclic structures. Taking all the results together allowed us to identify and characterize all the N···H hydrogen bonds, as well as the strain ring of the aziridine and its stability.

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Hydrogen Bonds and the Reactivity of Organic Compounds in Proton Transfer and Nucleophilic Substitution Reactions

Cited by 40 publications

References 2 publications

Strain‐Modulated Reactivity: An Acidic Silane

Strain‐Modulated Reactivity: An Acidic Silane

Interactions between bioactive ferulic acid and fumed silica by UV–vis spectroscopy, FT-IR, TPD MS investigation and quantum chemical methods

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

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