Tautomeric Equilibria in Relation to Pi‐Electron Delocalization

Raczyńska, Ewa D.; Kosinska, Wanda; Ośmiałowski, Borys; Gawinecki, Ryszard

doi:10.1002/chin.200604270

Cited by 26 publications

(48 citation statements)

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“…It is well known that tautomerism refers to an equilibrium between two or more different isomeric forms of the same compound called tautomers (Gold, 1979;Raczynska et al, 2005). This phenomenon exists in structures having more than one position to which the transferred proton can be bound.…”

Section: Introductionmentioning

confidence: 98%

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Safi

2016

Arabian Journal of Chemistry

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The results of a detailed DFT (B3LYP) investigation on five tautomers of thiazolidine-2,4-dione and their 5-substituted derivatives (ACH 3 , ANH 2 , ACl, AF, ACN-and NO 2 ) are presented here. The energy, geometrical parameters, topological parameters of all species in the gas phase have been calculated at B3LYP6-311++G(3df,2p)//B3LYP/311 + G(d,p) level of theory. The proton affinities (Pas), molecular electrostatic potential (MEP), natural valence atomic orbital energies (NNAO) of the basic center exist in the title compound in the gas phase have been calculated at the same level of theory. The specific hydration of the title compound by one water molecule has been also investigated at the same level of theory. Among the thiazolidine-2,4-dione tautomers and its derivatives, the most stable tautomer corresponds to the diketo forms (A), regardless of the substituent type. Results reveal that the oxygen atom of the carbonyl group at position 2 is more basic than the one at position 4. The existence of different hydrogen bond donor and acceptor centers in these molecules led to different kinds of intermolecular hydrogen bonds (CHAEAEAEO, NAHAEAEAEO and C‚OAEAEAEH) and different kinds of complexes. The stability of the cyclic complexes has been investigated using the analysis of Natural Bond Orbital (NBO), Atoms In Molecules topology, and the thermodynamic data. Results suggest that the water molecule prefers to bind with the oxygen atom, which has low intrinsic character. ª 2015 The Author. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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Section: Introductionmentioning

confidence: 98%

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Safi

2016

Arabian Journal of Chemistry

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“…Knowledge of the tautomeric preferences in organic molecules, especially in tetrazoles and triazoles, is of importance since their functionality or physicochemical activity may be tautomer sensitive [14][15][16][17]. A number of papers have been published concerning different triazole tautomers, solvent effects on the equilibria between them [18][19][20][21] as well as the proton transfer phenomena in azole-based coordination polymers [22]. However, to the best of our knowledge, UV-induced proton transfer between azole tautomers was not reported.…”

Section: Introductionmentioning

confidence: 83%

UV-induced proton transfer in 3-amino-1,2,4-triazole

Pagacz-Kostrzewa

Bil

Wierzejewska

2017

Journal of Photochemistry and Photobiology A: Chemistry

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“…This type of tautomerization is frequently the key step in important biological processes, where the energetically less stable tautomer is often responsible for the biological activity. 122 The extremely unstable pyridyl-2-ylidene was generated in the gas phase by Schwarz et al, and characterized by means of mass spectroscopy. 123 Pyridin-2-ylidines are more than 40 kcal•mol -1 less stable than pyridines, but coordination to transition metal fragments can strongly stabilize them.…”

Section: Tautomerization Of Pyridinesmentioning

confidence: 99%

Dearomatization of Transition Metal-Coordinated N-Heterocyclic Ligands and Related Chemistry

Arévalo

Espinal‐Viguri

Huertos

et al. 2016

Advances in Organometallic Chemistry

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Contents 1. Introduction 2. Addition of Main Group Organometallic Reagents to Pyridines and Related Heteroaromatics 3. Reaction of Pyridines with Early Transition Metal Complexes 4. The Elusive Nucleophilic Attack on Transition Metal-Coordinated 2,2'-Bipyridine and 1,10-Phenanthroline 5. Reactivity of Carbonyl rhenium and Molybdenum Complexes 5.1 Reactions of the Phosphido Complex [Re(PPh 2)(CO) 3 (phen)] with Activated Acetylenes and Olefins 5.2 Dearomatization by Deprotonation of Complexes with N-alkylimidazole Ligands 5.3 Couplings and Dearomatization Initiated by Deprotonation of C(sp 3)-H Bonds

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Tautomeric Equilibria in Relation to Pi‐Electron Delocalization

Cited by 26 publications

References 1 publication

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

UV-induced proton transfer in 3-amino-1,2,4-triazole

Dearomatization of Transition Metal-Coordinated N-Heterocyclic Ligands and Related Chemistry

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