A DFT study on protic solvent assisted tautomerization of heterocyclic thiocarbonyls

Jayasree, Elambalassery G.; Sreedevi, S.

doi:10.1016/j.chemphys.2019.110650

Cited by 13 publications

(10 citation statements)

References 33 publications

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“…NMR spectroscopy is a powerful technique for studying the tautomeric equilibria between the thiol (T SH ) and thione (T NH ) forms of novel thiohydantoins, as well as the relative contributions of these two forms. 46,47 Since all IMTH ligands have the same organic cation and consequently identical 1 H/ 13 C NMR spectra, therefore, the 1 H NMR spectrum of IMTH 2 (5b) (Fig. 2A), as a representative of all ligands, was extensively studied.…”

Section: Structural Characterizationmentioning

confidence: 99%

Novel imidazolium-thiohydantoin hybrids and their Mn(iii) complexes for antimicrobial and anti-liver cancer applications

et al. 2022

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Section: Structural Characterizationmentioning

confidence: 99%

Novel imidazolium-thiohydantoin hybrids and their Mn(iii) complexes for antimicrobial and anti-liver cancer applications

et al. 2022

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“…However, it has been reported previously that three or more polar protic solvents enhance the tautomerization reaction in the excited state via the hydrogen bonded network. 53,54 Please do not adjust margins…”

Section: Excited-state Hydrogen Transfer Barriersmentioning

confidence: 99%

Solvent Mediated Excited State Hydrogen Transfer in 6-Azaindole - S3,4 and 2,6-Diazaindole - S3,4 Clusters (S= H2O, NH3)

Baweja

Kalal

Mitra

et al. 2023

Preprint

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Excited state hydrogen (ESHT) and proton (ESPT) transfer pathways in the solvent clusters of 6-azaindole 6AI-S3,4 and 2,6-diazaindole 26DAI-S3,4 (S=H2O, NH3) were computationally explored to understand the fate of photo-excited biomolecules. The ESHT energy barriers in (H2O)3 complexes (39.6-41.3 kJmol-1) were decreased in (H2O)4 complexes (23.1-20.2 kJmol-1). Lengthening the solvent chain reduced the barrier because of the relaxed transition states geometries with reduced angular strains. Replacing the water molecule with ammonia drastically decreased the energy barriers to 21.4-21.3 kJmol-1 in (NH3)3 complexes and 8.1-9.5 kJ mol-1 in (NH3)4 complexes. The transition state was identified as Ha atom attached to the first solvent molecule. The formation of stronger hydrogen bonds in (NH3)3,4 complexes resulted in facile ESHT reaction than that in the (H2O)3,4 complexes. The ESPT energy barriers, in 6AI-S3,4 and 26DAI-S3,4 are found to range between 40-73 kJmol-1. The above values were significantly higher than that of the ESHT processes and hence are considered a minor channel in the process. The energetics of ESHT and ESPT explored in this study would be of great importance to study the photochemistry of N-rich biomolecules in the presence of various protic environments.

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“…The formation of 2a could be postulated considering two different pathways. It is known that thiohydantoin is in equilibrium with the thiol tautomer 20,21 ; for this reason, the nucleophilic attack to the alkyl group could be initiated either by the thiol group or the nitrogen lone pair of the thiohydantoin. To address this question, a reaction of 1-bromoethane with 1a was performed.…”

Section: Synthesismentioning

confidence: 99%

GFP-related chromophores: photoisomerization, thermal reversion, and DNA labelling

Faillace

Dolgopolova

Ceballos

et al. 2023

Phys. Chem. Chem. Phys.

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A DFT study on protic solvent assisted tautomerization of heterocyclic thiocarbonyls

Cited by 13 publications

References 33 publications

Novel imidazolium-thiohydantoin hybrids and their Mn(iii) complexes for antimicrobial and anti-liver cancer applications

Novel imidazolium-thiohydantoin hybrids and their Mn(iii) complexes for antimicrobial and anti-liver cancer applications

Solvent Mediated Excited State Hydrogen Transfer in 6-Azaindole - S3,4 and 2,6-Diazaindole - S3,4 Clusters (S= H2O, NH3)

GFP-related chromophores: photoisomerization, thermal reversion, and DNA labelling

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