Energetics of 1-(aminophenyl)pyrroles: A joint calorimetric and computational study

Santos, Ana Filipa L.O.M.; Silva, Manuel A.V. Ribeiro da

doi:10.1016/j.jct.2011.04.022

Cited by 12 publications

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“…Following our studies on the thermodynamic and thermochemical properties of several substituted pyrroles and their relationship with the corresponding molecular structures, − which are intended to be used as a building blocks of porphyrins, polypyrroles, and drugs with high therapeutical potential, we report, in the present work, an experimental and computational study on the energetic and structural properties of several alkyl pyrrolecarboxylates (alkyl = methyl or ethyl). It is of great importance for the understanding of the activity and behavior of large molecules to know the molecular energetics of its fragments.…”

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confidence: 99%

Molecular Energetics of Alkyl Pyrrolecarboxylates: Calorimetric and Computational Study

Santos

Silva

2013

J. Phys. Chem. A

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The pyrrole subunit plays an important role in material science as the building block of polypyrroles, an important representative class of conducting polymers, which found widely applications in the area of new materials due to their chemical, thermal, and electrical properties associated with their easiness and low cost of production, making them especially promising for commercial applications. The energetic characterization of this kind of molecules provides information concerning stability, reactivity, and biodegrability of chemical compounds in environment being, for example, helpful in choosing the most adequate method for their elimination by converting the waste into harmless compounds or even decreasing the production of toxic substances in industrial processes. This work reports a combination of calorimetric and computational determinations of several alkyl pyrrolecarboxylates (alkyl = methyl or ethyl) whose main purpose is the calculation of their standard (p° = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T = 298.15 K. Experimentally, for methyl 1-pyrrolecarboxylate (M1PC), methyl 2-pyrrolecarboxylate (M2PC), and ethyl 2-pyrrolecarboxylate (E2PC), these values were derived from the standard (p° = 0.1 MPa) molar enthalpies of formation, in the condensed phase, ΔfHm° (cr,l), at T = 298.15 K, obtained by static bomb combustion calorimetry, and from the standard molar enthalpies of phase transition, Δcr,l(g)Hm°, at T = 298.15 K, determined by high-temperature Calvet microcalorimetry. Standard ab initio molecular calculations, at the G3(MP2)//B3LYP level, were performed, and the standard enthalpies of formation of these three compounds were estimated. A very good agreement between the calculated and the experimental data was obtained. Thereby, we have extended these calculations to other alkyl pyrrolecarboxylates, namely, ethyl 1-pyrrolecarboxylate (E1PC), methyl 3-pyrrolecarboxylate (M3PC), and ethyl 3-pyrrolecarboxylate (E3PC), whose study was not performed experimentally. The computational analysis, at the B3LYP/6-31G(d) level of theory, of the six molecules allowed a detailed inspection and a better knowledge about their molecular structure and geometrical parameters.

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Section: Introductionmentioning

confidence: 99%

Molecular Energetics of Alkyl Pyrrolecarboxylates: Calorimetric and Computational Study

Santos

Silva

2013

J. Phys. Chem. A

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Thermochemical Insights on Small Nitrogen Heterocyclic Compounds

Freitas

Silva

2019

Patai's Chemistry of Functional Groups

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Along this overview, a comprehensive thermochemical discussion of small nitrogen heterocyclic molecules is presented, based on reliable information obtained by experimental and computational methodologies. Calorimetric data jointly with other data obtained from alternative sources are used to acquire extensive thermochemical information. A brief description is provided on the more common techniques used in the measurement of properties of compounds under analysis, as well as fundaments on methodologies used in computational approaches, to establish alternative strategies to derive data for other species. Data analysis is fundamentally focused on the standard molar enthalpy of formation, an essential thermodynamic parameter to assess the energy associated to chemical reactions or other transformations involving the compounds, also allowing to derive related thermodynamic properties. This study focuses on neutral, π conjugated, nitrogen heterocyclic five‐membered systems with 1–4 heteroatoms, and some substituted derivatives, complemented by a short discussion on other species having one benzenic ring fused to the heterocycle. Considering its role on chemical structure and reactivity properties, the establishment of intermolecular hydrogen bonding deserved special attention. Complementarily, NH bond dissociation enthalpy values along different aza systems are analyzed and used on comparing thermodynamic favorability of corresponding bond disruptions. An enthalpic parameters database for the selected groups of compounds is reportedly commented, gauging about their reliability to be assumed as key values.

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The influence of methyl groups on the torsion angle and on the energetics of 1-phenylpyrrole derivatives: a thermodynamic and computational study

Santos

Silva

2013

Struct Chem

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Energetics of 1-(aminophenyl)pyrroles: A joint calorimetric and computational study

Cited by 12 publications

References 25 publications

Molecular Energetics of Alkyl Pyrrolecarboxylates: Calorimetric and Computational Study

Molecular Energetics of Alkyl Pyrrolecarboxylates: Calorimetric and Computational Study

Thermochemical Insights on Small Nitrogen Heterocyclic Compounds

The influence of methyl groups on the torsion angle and on the energetics of 1-phenylpyrrole derivatives: a thermodynamic and computational study

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