Theoretical investigation on the tautomerization mechanism of phosphinic acids

Vincze, Daniella; Bagi, Péter; Ábrányi‐Balogh, Péter

doi:10.1080/10426507.2018.1543303

Cited by 7 publications

(9 citation statements)

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“…The second possibility would require tautomerization of 3H 2 to the P(III) species 3H that could undergo nucleophilic attack and proton transfer steps in a stepwise or concerted fashion (Scheme 2: bottom). The P(V) -P(III) tautomerization is well established, [33,[36][37][38][39] which supports the viability of both 3H 2 and 3H as intermediates.…”

Section: Chemistry-a European Journalmentioning

confidence: 55%

Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines

Lamberink

Boyle

Gilroy

et al. 2022

Chemistry A European J

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Reactivity of primary phosphines with two stoichiometric equivalents of imine results in the formation of bis-αaminophosphines (2 a-e), which can be subsequently oxidized in the presence of S 8 or H 2 O 2 to generate air stable bisα-aminophosphine sulfides (2 b-m(S/O)). To elucidate the mechanism of this three-component reaction, Hammett analysis, kinetic isotope effect (KIE), and trapping experiments were performed. Ultimately a P(V)-P(III) tautomerization is invoked, followed by nucleophilic attack by the P(III) species to generate the desired products.

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Section: Chemistry-a European Journalmentioning

confidence: 55%

Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines

Lamberink

Boyle

Gilroy

et al. 2022

Chemistry A European J

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“…In order to broaden the characterization of the tautomerism of >P(O)H derivatives, and as a continuation of our efforts [23] to obtain mechanistic insights into the reactivity of P -species, we performed systematic quantum chemical computations on a series of acyclic >P(O)H derivatives using the Gaussian 09 program package [24] to apply various methods, basis sets, and taking into account the effect of a wide range of solvents. Our intent was to study the effect of these solvents and to explain the observed phenomena with different molecular descriptors as physical chemical parameters.…”

Section: Introductionmentioning

confidence: 99%

A Mechanistic Study on the Tautomerism of H-Phosphonates, H-Phosphinates and Secondary Phosphine Oxides

et al. 2019

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H-phosphonates, H-phosphinates and secondary phosphine oxides may be preligands, and are important building blocks in the synthesis of pharmaceuticals, pesticides, and P-ligands. The prototropic tautomerism influenced by substituent effects plays an important role in the reactivity of these species. The main goal of our research was to study the tautomerism of the >P(O)H reagents by means of computational investigations applying several DFT methods at different levels. We focused on the effect of implicit solvents, and on explaining the observed trends with physical chemical molecular descriptors. In addition, multiple reaction pathways incorporating three P-molecules were elucidated for the mechanism of the interconversion.

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“…This factor could significantly hamper the chlorination reaction, therefore, in order to estimate the tautomerisation barrier, the energy profile of the two types of conversion from pentavalent tert-butyl(phenyl)phosphine oxide (1) to its tautomeric trivalent form were examined. As previously proven for dimethylphosphine oxide, it can tautomerize to its trivalent form in two ways [37] . Route 1 -where one molecule of phosphine oxide is engaged in transferring a proton from its phosphorus atom to oxygen.…”

Section: Theoretical Section Considered Mechanismmentioning

confidence: 76%