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Stabilizing Effect of a 4c/6e Hypervalent Bond in Dinitrodiphenyl Disulfides and Their Thermochemical Properties: Experimental and Computational Approach.
Flores, Henoc; Ramos, Fernando; Hernández-Pérez, Julio M; Solano-Altamirano, Juan M; Camarillo, E Adriana; Sandoval-Lira, Jacinto.
Afiliação
  • Flores H; Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P. 72570 Puebla Pue., Mexico.
  • Ramos F; Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P. 72570 Puebla Pue., Mexico.
  • Hernández-Pérez JM; Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P. 72570 Puebla Pue., Mexico.
  • Solano-Altamirano JM; Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P. 72570 Puebla Pue., Mexico.
  • Camarillo EA; Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P. 72570 Puebla Pue., Mexico.
  • Sandoval-Lira J; Departamento de Ingeniería Ambiental, Instituto Tecnológico Superior de San Martín Texmelucan, C.P. 74120 San Martín Texmelucan, Pue., Mexico.
J Phys Chem A ; 127(26): 5534-5546, 2023 Jul 06.
Article em En | MEDLINE | ID: mdl-37365903
Thermochemical properties and intramolecular interactions of 2,2'-dinitrodiphenyl disulfide (2DNDPDS) and 4,4'-dinitrodiphenyl disulfide (4DNDPDS) were determined and analyzed. Their standard molar formation enthalpies in the gas phase (ΔfHm°(g)'s) were experimentally determined; theoretically, they were computed using the G4 composite method and atomization reactions. Specifically, ΔfHm°(g)'s were obtained by combining formation enthalpies in the condensed phase and enthalpies of phase change. Formation enthalpies in the condensed phase were determined experimentally through combustion energies, which in turn were found by means of a rotatory bomb combustion calorimeter. Sublimation enthalpies were derived from thermogravimetric experiments, measuring the rate of mass loss and using Langmuir and Clausius-Clapeyron equations. Fusion enthalpies and heat capacities of the solid and liquid phases were measured as functions of temperature by differential scanning calorimetry, and the heat capacities of the gas phase were calculated via molecular orbital calculations. Theoretical and experimental ΔfHm°(g)'s differed by <5.5kJ·mol-1, and isomerization enthalpies are discussed. In addition, using theoretical tools [natural bond orbitals (NBO) and quantum theory of atoms in molecules (QTAIM)], intramolecular interactions were analyzed. An uncommon hypervalent four-center six-electron interaction of type O···S-S···O was found in 2DNDPDS. This hypervalent interaction, in addition to the extent of conjugation between the aryl and NO2 moieties and the formation of intramolecular C-H···S hydrogen bonds, counteracts the repulsion caused by steric repulsions. Hydrogen bonding was confirmed through geometric parameters as well as QTAIM.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article