title: Calorimetric and computational thermochemical study of 3,3-tetramethyleneglutaric acid, 3,3-tetramethyleneglutaric anhydride, and 3,3-tetramethyleneglutarimide.
abstract: The standard (p(o) = 0.1 MPa) molar energies of combustion in oxygen, at T = 298.15 K, of solid 3,3-tetramethyleneglutaric acid and the related 3,3-tetramethyleneglutaric anhydride and 3,3-tetramethyleneglutarimide were measured by static bomb combustion calorimetry. The values of the standard molar enthalpies of sublimation, at T = 298.15 K, were obtained by Calvet microcalorimetry, allowing the calculation of the standard molar enthalpies of formation of the compounds, in the gaseous state, at T = 298.15 K. The geometries of the experimentally studied compounds were fully optimized using density functional theory with the B3LYP functional and extended basis sets. More accurate energies were also obtained from single-point calculations at the most stable B3LYP/6-311G** geometries, using the cc-pVTZ basis set. From these calculations the standard molar enthalpies of formation of 3,3-tetramethyleneglutaric acid, 3,3-tetramethyleneglutaric anhydride, and 3,3-tetramethyleneglutarimide were estimated using isodesmic reactions involving glutaric acid, glutaric anhydride, and glutarimide, respectively. Experimental and computational results were used in the discussion of the interrelation of energetics and structure in these compounds and compared with other structurally related compounds.
authors.affiliation: Centro de Investigação em Química, Departamento de Química, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre 687, P-4169-007 Porto, Portugal. marmatos@fc.up.pt
authors.forename: M Agostinha R
authors.initials: MA
authors.lastname: Matos
authors.forename: Margarida S
authors.initials: MS
authors.lastname: Miranda
authors.forename: Diana A P
authors.initials: DA
authors.lastname: Fonseca
authors.forename: Victor M F
authors.initials: VM
authors.lastname: Morais
authors.forename: Joel F
authors.initials: JF
authors.lastname: Liebman
mesh_terms: D002151:Calorimetry; D005977:Glutarates / Q000737:chemistry*; D010881:Piperidones / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: C533177:3,3-tetramethyleneglutarimide; D005977:Glutarates; D010881:Piperidones; C060318:tetramethylene glutaric acid