Conformations of some 2-substituted furan and thiophen carbonyl compounds

Cheng, C. L.; John, Ian G.; Ritchie, G. L. D.; Gore, P. H.; Farnell, L.

doi:10.1039/p29750000744

Cited by 36 publications

(13 citation statements)

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“…For some of the diheteroaryl ketones and thioketones considered here, their conformational behavior has previously been studied experimentally [10][11][12][13]. From dipole moment measurements, it is inferred that the cc-conformation is preferred for 2a [10].…”

Section: Introductionmentioning

confidence: 98%

“…According to an early experimental dipole moment measurement for the preferred conformer of 2a in solution, a dihedral angle of 45°± 10°between the planes of two 2-thiophenyl rings has been inferred [10]. A more recent experimental study of the crystal structure of 2a reports that the S-C-C=O angle in the cc-conformer amounts to -21.6° [13].…”

Section: Geometriesmentioning

confidence: 99%

“…The greatest stabilization of the cc-conformation by the E NL component can be clarified in terms of electron delocalization. Strictly speaking, a significant p-conjugation is expected for a trans arrangement of the C=Y bond and the adjacent C=C bond of the heterocyclic ring (for this bond, there is a high p-electron density) [10,61]. This p-conjugation can be illustrated by the energies of specific donoracceptor interactions E (2) estimated using a standard second-order perturbation treatment [33].…”

Section: Nbo Analysismentioning

confidence: 99%

“…From dipole moment measurements, it is inferred that the cc-conformation is preferred for 2a [10]. A more recent analysis of the dipole moments of 2a and 2b in benzene solutions suggests a mixture of cc-conformer and mixed conformers, with the former being more abundant (72 and 91 % for 2a and 2b, respectively) [11].…”

Section: Introductionmentioning

confidence: 99%

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Conformers of diheteroaryl ketones and thioketones: a quantum chemical study of their properties and fundamental intramolecular energetic effects

Matczak

Domagała

2015

Struct Chem

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The conformational behavior of ten diheteroaryl ketones and thioketones is investigated using various quantum chemical methods. These ketones and thioketones are formed by the disubstitution of formaldehyde and thioformaldehyde with such a heteroaryl group as 2-furanyl, 2-thiophenyl, 2-selenophenyl, 2-pyrrolyl or 1-methyl-2-pyrrolyl. For these compounds, their conformational preference and the energetic ordering of their conformers are determined at the MP2 and B3LYP levels of theory. Energetic barriers resulting from the interconversion between conformations are also estimated. The natural bond orbital (NBO) and interacting quantum atoms (IQA) methods are used to study fundamental intramolecular energetic effects influencing the stability of individual conformers. The results of the two methods indicate the great significance of the effect associated with electron delocalization (in the form of either NBO donor-acceptor interactions or the IQA interatomic exchange-correlation interaction energy) in governing the conformational behavior of the investigated diheteroaryl ketones and thioketones.

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Section: Introductionmentioning

confidence: 98%

Section: Geometriesmentioning

confidence: 99%

Section: Nbo Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Conformers of diheteroaryl ketones and thioketones: a quantum chemical study of their properties and fundamental intramolecular energetic effects

Matczak

Domagała

2015

Struct Chem

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“…9,10 Computational studies proved that the conformation of these molecules are the result of the interaction between the electronic pair of the oxygen in the carbonyl group and the heteroatom in the neighboring ring, indicating a favored conformation. [11][12][13] Electrochemical studies showed the existence of irreversible and asymmetrical peaks. This behavior was explained by the simultaneous oxidation of the heterocyclic rings and the functional groups acting as bridges.…”

Section: Introductionmentioning

confidence: 99%