Malondialdehyde and acetylacetone. An AM1 study of their molecular structures and keto–enol tautomerism

Buemi, Giuseppe; Gandolfo, C.

doi:10.1039/f29898500215

Cited by 64 publications

(25 citation statements)

References 5 publications

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“…Nevertheless, in spite of this, some additive schemes leading to numbers understood as interaction energies have been proposed. Among them, the so-called open-closed method [45,46] seems to be both the most popular [26][27][28][29][45][46][47][48][49][50][51][52][53][54][55][56][57][58] and straightforward. According to this method, the interaction energy is just a difference between total energies of the closed form of a molecule, i.e.…”

Section: Energy Of An Intramolecular Interactionmentioning

confidence: 99%

Strength of Si–H ⋯ B charge-inverted hydrogen bonds in 1-silacyclopent-2-enes and 1-silacyclohex-2-enes

Jabłoński

2017

Struct Chem

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It is shown that the H· · · B contacts in 1-silacyclohex-2-enes are clearly stabilizing and strong, whereas those in 1-silacyclopent-2-enes are much weaker. This result is supported by analysis of QTAIM-based parameters and appropriate structural changes taking place upon the open form → closed form transformation and is in full agreement with previous NMR spectroscopic data [Wrackmeyer et al. (2006) Appl Organometal Chem 20:99-105]. Also, the influence of electronic and steric effects originating from the presence of specific substituents on the strength of the H· · · B contacts is discussed in detail. Some problems and ideas associated with the use of the so-called open-closed method utilized in assessing values of interaction energies are discussed in detail. Particular attention is paid to the correct choice of reference open systems. It is shown that their partial geometry optimization leads to reliable values of interaction energies.

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Section: Energy Of An Intramolecular Interactionmentioning

confidence: 99%

Strength of Si–H ⋯ B charge-inverted hydrogen bonds in 1-silacyclopent-2-enes and 1-silacyclohex-2-enes

Jabłoński

2017

Struct Chem

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“…With respect to the cis-enol forms of b-diketone, several phenomena suggesting a proton transfer between the two enol forms ( -and -forms) as represented in have been reported [11][12][13][14][15] . However, the phenomena have been also explained by the existence of the resonance structure, , shown in [16][17][18][19] .…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Hydrogen Bonding (Proton Transfer) of 1-Phenyl-1,3-butanedione

Matsuzawa¹,

Nakagaki²,

Iwahashi³

2007

J. Oleo Sci.

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Through the 1 H and 13 C NMR measurements for the symmetrical b-diketones such as 2,4-pentanedione and 1,3-diphenyl-1,3-propanedione and unsymmetrical one such as 1-phenyl-1,3-butanedione at various concentrations and temperatures, we confirmed that 1-phenyl-1,3-butanedione in CDCl 3 exists as monomers in its relatively low concentration. In addition, the 1-phenyl-1,3-butanedione in CDCl 3 exists not as a keto-form but as two kinds of cis-enol forms. The proton transfer between the two kinds of cis-enols for 1-phenyl-1,3-butanedione was discussed thermodynamically; it is concluded that the OH proton of enol of 1-phenyl-1,3-butanedione is considerably located near the oxygen atom attached to the carbon atom linking to a phenyl group.

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“…It should be noted that work allowing a direct comparison of the two molecules, i.e. using same experimental or theoretical methods, are a very few [39][40][41].…”

Section: Introductionmentioning

confidence: 99%

Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices

Trivella¹,

Coussan²,

Chiavassa³

et al. 2006

Low Temperature Physics

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Structure and reactivity of the eight enolic forms (one chelated and seven non-chelated) of malonaldehyde and acetylacetone are compared through theoretical and experimental data. Ground-state geometries, energies, and vibrational frequencies are calculated with the B3LYP/6-311++G(2d,2p) model chemistry. The electronic delocalisation as well as the cis/trans rotamer properties are analysed. The hydrogen bond strength of the chelated forms can be estimated by the energy difference between chelated and non-chelated forms, and its enhancement due to methyl-induced electron release is estimated at 1.7 kcal·mol -1 . UV-and IR-induced reactivity of molecules isolated in nitrogen matrices is studied by means of FT-IR spectrometry. Interconversion between rotamers is the main process observed for both molecules, only some among the seven non-chelated forms being created.PACS: 36.20.Ng, 31.15.Ar

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Malondialdehyde and acetylacetone. An AM1 study of their molecular structures and keto–enol tautomerism

Cited by 64 publications

References 5 publications

Strength of Si–H ⋯ B charge-inverted hydrogen bonds in 1-silacyclopent-2-enes and 1-silacyclohex-2-enes

Strength of Si–H ⋯ B charge-inverted hydrogen bonds in 1-silacyclopent-2-enes and 1-silacyclohex-2-enes

Intramolecular Hydrogen Bonding (Proton Transfer) of 1-Phenyl-1,3-butanedione

Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices

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